Methods of forming single source precursors, methods of forming polymeric single source precursors, and single source precursors formed by such methods

ABSTRACT

Methods of forming single source precursors (SSPs) include forming intermediate products having the empirical formula ½{L 2 N(μ-X) 2 M′X 2 } 2 , and reacting MER with the intermediate products to form SSPs of the formula L 2 N(μ-ER) 2 M′(ER) 2 , wherein L is a Lewis base, M is a Group IA atom, N is a Group IB atom, M′ is a Group IIIB atom, each E is a Group VIB atom, each X is a Group VIIA atom or a nitrate group, and each R group is an alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl, silane, or carbamato group. Methods of forming polymeric or copolymeric SSPs include reacting at least one of HE 1 R 1 E 1 H and MER with one or more substances having the empirical formula L 2 N(μ-ER) 2 M′(ER) 2  or L 2 N(μ-X) 2 M′(X) 2  to form a polymeric or copolymeric SSP. New SSPs and intermediate products are formed by such methods.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.13/659,620, filed Oct. 24, 2012, pending, which is a divisional of U.S.patent application Ser. No. 12/646,474, filed Dec. 23, 2009, now U.S.Pat. No. 8,324,414, issued Dec. 4, 2012, the subject matter of which isrelated to the subject matter of U.S. patent application Ser. No.13/191,062, filed Jul. 26, 2011, to the subject matter of U.S. patentapplication Ser. No. 13/099,043, filed May 2, 2011, now U.S. Pat. No.8,445,388, issued May 21, 2013, which application is a divisional ofU.S. patent application Ser. No. 12/047,956, filed Mar. 13, 2008, nowU.S. Pat. No. 8,003,070, issued Aug. 23, 2011, to the subject matter ofU.S. patent application Ser. No. 13/019,879, filed Feb. 2, 2011, and tothe subject matter of U.S. patent application Ser. No. 13/365,800, filedFeb. 3, 2012. The disclosure of each of the foregoing applications andpatents is hereby incorporated herein in its entirety by this reference.

GOVERNMENT RIGHTS

This invention was made under a Cooperative Research and DevelopmentAgreement between Precision Nanoparticles and Battelle Energy Alliance,LLC under Contract Number DE-AC07-05ID14517 awarded by the United StatesDepartment of Energy. The government has certain rights in thisinvention.

TECHNICAL FIELD

Embodiments of the invention relate to methods of forming single sourceprecursors and, more particularly, to methods of forming organometallicsingle source precursors for use in forming semiconductor materials,particles, and devices.

BACKGROUND

Semiconductor devices are devices that employ semiconductor materials,which are solid materials that exhibit an electrical conductivity lyingbetween that of a conductor and that of an insulator. Semiconductordevices include, for example, diodes (e.g., light emitting diodes(LEDs)), photovoltaic devices, sensors, solid state lasers, andintegrated circuits (e.g., memory modules and microprocessors).

Semiconductor materials that can be employed in semiconductor devicesinclude, for example, silicon (Si), germanium (Ge), chalcopyrites (e.g.,CuInS₂, CuGaS₂, and CuInSe₂), chalcogenides (e.g.,Cu(In_(x)Ga_(1-x))(Se_(y)S_(1-y))₂), cadmium telluride (CdTe), galliumarsenide (GaAs), organic polymers (e.g., polyphenylene vinylene, copperphthalocyanine, fullerenes), and light absorbing dyes (e.g.,ruthenium-centered metalorganic dyes).

It has been discovered that chalcopyrite materials may be formed bydecomposing one or more so-called “single source precursors” (SSPs),which are organometallic substances (e.g., molecules, complexes, etc.)that comprise all of the atomic elements, in the appropriatestoichiometric ratios, necessary to form a chalcopyrite material. Suchmethods, and methods of forming such SSPs are disclosed in, for example,Hirpo et al., Synthesis of Mixed Copper-Indium Chalcogenolates.Single-Source Precursors for The Photovoltaic Materials CuInQ ₂ (Q=S,Se), JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 115, Iss. 4, pp.1597-1599 (Feb. 24, 1993). Methods for forming such SSPs are alsodisclosed in, for example, U.S. Pat. No. 6,992,202, which issued Jan.31, 2006 to Banger et al.

There remains a need in the art, however, for improved methods that maybe used to form single source precursors for use in forming chalcopyritematerials (e.g., semiconductive ternary chalcopyrite materials).

BRIEF SUMMARY

In some embodiments, the present invention includes methods of formingsingle source precursors. The methods include fanning an intermediateproduct having the empirical formula ½{L₂N(μ-X)₂M′X₂}₂, and reacting MERwith the intermediate product to form a single source precursor havingthe empirical formula L₂N(μ-ER)₂M′(ER)₂, wherein L is a Lewis basecoordinated to N by a dative bond, each M is individually selected fromGroup IA atoms, each N is individually selected from Group IB atoms,each M′ is individually selected from Group IIIA atoms, each E isindividually selected from Group VIA atoms, each X is individuallyselected from Group VIIA atoms or a nitrate group, and each R group isindividually selected from the group consisting of alkyl, aryl, vinyl,(per)fluoro alkyl, (per)fluoro aryl, silane, and carbamato groups.

In some embodiments, the present invention includes methods of formingsingle source precursors from other single source precursors. Forexample, HE²R² may be reacted with a first single source precursorhaving the empirical formula L₂N(μ-E¹R¹)₂M′(E¹R¹)₂ to form a second,different single source precursor having the empirical formulaL₂N(μ-E²R²)₂M′(E²R²)₂, wherein L is a Lewis base coordinated to N by adative bond, each N is individually selected from Group IB atoms, eachM′ is individually selected from Group IIIA atoms, each E¹ and E² isindividually selected from Group VIA atoms, and each R¹ and R² group isindividually selected from the group consisting of alkyl, aryl, vinyl,(per)fluoro alkyl, (per)fluoro aryl, silane, and carbamato groups.

In additional embodiments, the present invention includes methods offorming polymeric single source precursors, in which HE¹R¹E¹H is reactedwith a single source precursor having the empirical formulaL₂N(μ-ER)₂M′(ER)₂ to form a polymeric single source precursor having theempirical formula[L₂N(μ-ER)_(a)(μ-E¹R¹E¹)_(b)M′(ER)_(c)(E¹R¹E¹)_(d)]_(m), wherein L is aLewis base coordinated to N by a dative bond, each N is individuallyselected from Group IB atoms, each M′ is individually selected fromGroup IIIA atoms, each E and E¹ is individually selected from Group VIAatoms, a is any number from zero (0) to two (2), b is the differencebetween two (2) and a (b=2−a), c is any number from zero (0) to two (2),d is the difference between two (2) and c (d=2−c), m is any number, eachof the R groups is individually selected from the group consisting ofalkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl, silane, andcarbamato groups, and each of the R¹ groups is individually selectedfrom the group consisting of aryl, vinyl, (per)fluoro alkyl, (per)fluoroaryl, silane, carbamato, and α,ω-E¹ functionalized alkyl groups.

In additional embodiments, the present invention includes methods offorming polymeric single source precursors in which at least one ofHE¹R¹E¹H and HE²R² is reacted with a single source precursor having theempirical formula L₂N(μ-ER)₂M′(ER)₂ to form a polymeric single sourceprecursor having the empirical formula[L₂N(E²R²)_(a)(μ-E¹R¹E¹)_(b)M′(E²R²)_(c)(E¹R¹E¹)_(d)]_(m), wherein L isa Lewis base coordinated to N by a dative bond, each N is individuallyselected from Group IB atoms, each M′ is individually selected fromGroup IIIA atoms, each E, E¹, and E² is individually selected from GroupVIA atoms, a is any number from zero (0) to two (2), b is the differencebetween two (2) and a, c is any number from zero (0) to two (2), d isthe difference between two (2) and c, m is any number, each R and R² isindividually selected from the group consisting of alkyl, aryl, vinyl,(per)fluoro alkyl, (per)fluoro aryl, silane, and carbamato groups, andeach R¹ is individually selected from the group consisting of aryl,vinyl, (per)fluoro alkyl, (per)fluoro aryl, silane, carbamato, andα,ω-E¹ functionalized alkyl groups.

In yet further embodiments, the present invention includes methods offoil ling copolymeric single source precursors in which a first singlesource precursor, a second single source precursor differing from thefirst single source precursor, and HE¹R¹E¹H are reacted to form acopolymeric single source precursor having the empirical formula{[L₂N¹(ER)_(a)(μ-E¹R¹E¹)_(b)M′¹(ER)(E¹R¹E¹)_(d)]_(m)[L₂N²(ER)_(e)(μ-E¹R¹E¹)_(f)M′²(ER)_(g)(E¹R¹E¹)_(h)]_(n)}_(l),wherein L is a Lewis base, each N¹ and N² is individually selected fromGroup IB atoms, each M′¹ and M′² is individually selected from GroupIIIA atoms, each E and E¹ is individually selected from Group VIA atoms,a is any number from zero (0) to two (2), b is the difference betweentwo (2) and a, c is any number from zero (0) to two (2), d is thedifference between two (2) and c, e is any number from zero (0) to two(2), f is the difference between two (2) and e, g is any number fromzero (0) to two (2), h is the difference between two (2) and g, m is anynumber, n is any number, l is any number, each R is individuallyselected from the group consisting of alkyl, aryl, vinyl, (per)fluoroalkyl, (per)fluoro aryl, silane, and carbamato groups, and each R¹ isindividually selected from the group consisting of aryl, vinyl,(per)fluoro alkyl, (per)fluoro aryl, silane, carbamato, and α,ω-E¹functionalized alkyl groups.

Additional embodiments of the present invention include methods offorming polymeric single source precursors in which at least one ofME¹R¹E¹M and MER is reacted with a substance having the empiricalformula L₂N(μ-X)₂M′(X)₂ to form a polymeric single source precursorhaving the empirical formula[L₂N(μ-ER)_(a)(μ-E¹R¹E¹)_(b)M′(ER)_(c)(E¹R¹E¹)_(d)]_(m), wherein L is aLewis base that is coordinated to N by a dative bond, each M isindividually selected from Group IA atoms, each N is individuallyselected from Group IB atoms, each M′ is individually selected fromGroup IIIA atoms, each E and E¹ is individually selected from Group VIAatoms, each X is individually selected from Group VIIA atoms or anitrate group, a is any number from zero (0) to two (2), b is thedifference between two (2) and a (b=2−a), c is any number from zero (0)to two (2), d is the difference between two (2) and c (d=2−c), m is anynumber, each of the R groups is individually selected from the groupconsisting of alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl,silane, and carbamato groups, and each of the R¹ groups is individuallyselected from the group consisting of aryl, vinyl, (per)fluoro alkyl,(per)fluoro aryl, silane, carbamato, and α,ω-E¹ functionalized alkylgroups.

In additional embodiments, copolymeric single source precursors areformed by reacting uME¹R¹E¹M and vMER with a first substance having theempirical formula L₂N¹(μ-X)₂M′¹(X)₂ and a second substance having theempirical formula L₂N²(μ-X)₂M′²(X)₂ to form a copolymeric single sourceprecursor having the empirical formula{[L₂N¹(ER)_(a)(μ-E¹R¹E¹)_(b)M′¹(ER)_(c)(E¹R¹E¹)_(d)]_(m)[L₂N²(ER)_(e)(μ-E¹R¹E¹)_(f)M′²(ER)_(g)(E¹R¹E¹)_(h)]_(n)}_(l),wherein L is a Lewis base, each N¹ and N² is individually selected fromGroup IB atoms, each M′¹ and M′² is individually selected from GroupIIIA atoms, each E and E¹ is individually selected from Group VIA atoms,a is any number from zero (0) to two (2), b is the difference betweentwo (2) and a, c is any number from zero (0) to two (2), d is thedifference between two (2) and c, e is any number from zero (0) to two(2), f is the difference between two (2) and e, g is any number fromzero (0) to two (2), h is the difference between two (2) and g, m is anynumber, n is any number, l is any number, u is any number from zero (0)to four (4), v is the difference between four (4) and u, each R isindividually selected from the group consisting of alkyl, aryl, vinyl,(per)fluoro alkyl, (per)fluoro aryl, silane, and carbamato groups, andeach R¹ is individually selected from the group consisting of aryl,vinyl, (per)fluoro alkyl, (per)fluoro aryl, silane, carbamato, andα,ω-E¹ functionalized alkyl groups.

Further embodiments of the present invention include single sourceprecursors, polymeric single source precursors, and copolymeric singlesource precursors formed by the methods described herein.

For example, in some embodiments, the present invention includespolymeric, organometallic single source precursor having the empiricalformula [L₂N(ER)_(a)(μ-E¹R¹E¹)_(b)M′(ER)_(c)(E¹R¹E¹)_(d)]_(m), wherein Lis a Lewis base, each N is individually selected from Group IB atoms,each M′ is individually selected from Group IIIA atoms, each E and E¹ isindividually selected from Group VIA atoms, a is any number from zero(0) to two (2), b is the difference between two (2) and a, c is anynumber from zero (0) to two (2), d is the difference between two (2) andc, m is any number, each R is individually selected from the groupconsisting of alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl,silane, and carbamato groups, and each R¹ is individually selected fromthe group consisting of aryl, vinyl, (per)fluoro alkyl, (per)fluoroaryl, silane, carbamato, and α,ω-E¹ functionalized alkyl groups.

Yet further embodiments of the present invention include polymeric,organometallic single source precursors having the empirical formula[L₂N(μER¹)_(a)(μ-ER²E)_(b)M′(ER¹)_(c)(ER²E)_(d)]_(m), wherein L is aLewis base, each N is individually selected from Group IB atoms, each M′is individually selected from Group IIIA atoms, each E is individuallyselected from Group VIA atoms, a is any number from zero (0) to two (2),b is the difference between two (2) and a (b=2−a), c is any number fromzero (0) to two (2), d is the difference between two (2) and c (d=2−c),m is any number, each of the R¹ groups is individually selected from thegroup consisting of alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoroaryl, silane, and carbamato groups, and each of the R² groups isindividually selected from the group consisting of alkyl, vinyl, andaryl groups.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

While the specification concludes with claims particularly pointing outand distinctly claiming that which is regarded as the present invention,advantages of this invention may be more readily ascertained from thefollowing description of the invention when read in conjunction with theaccompanying drawings in which:

FIGS. 1 through 4 illustrate various intermediate products that may beformed in accordance with embodiments of methods of the presentinvention for forming single source precursors; and

FIG. 5 illustrates one example of a single source precursor that may beformed using methods of the present invention.

DETAILED DESCRIPTION

The illustrations presented herein are not meant to be actual views ofany particular molecule or complex, but are merely idealizedrepresentations that are employed to describe various embodiments of thepresent invention.

The chalcogens are the elements in Group VIA (16) of the periodic table.As used herein, the teen “chalcogenide” means and includes any compoundthat contains at least one chalcogen element other than oxygen (e.g.,sulfur, selenium, tellurium, etc.). Chalcogenides include, for example,ternary chalcopyrite materials.

As used herein the term “ternary chalcopyrite material” means andincludes any material having a composition generally represented by theformula I-III-VI₂, where roman numeral I refers to elements in Group I(Groups IA (1) and IB (11)) of the periodic table, roman numeral IIIrefers to elements in Group III (Groups IIIB (3) and IIIA (13)) of theperiodic table, and roman numeral VI refers to elements in Group VI(Groups VIB (6) and VIA (16)) of the periodic table. By ternary, it ismeant that the chalcopyrite materials contain atoms from three elementalGroups of the periodic table. For example, approximately twenty-fivepercent (25%) of the atoms in a ternary chalcopyrite material may befrom Group IB, approximately twenty-five percent (25%) of the atoms maybe from Group IIIA, and approximately fifty percent (50%) of the atomsmay be from Group VIA. CuInS₂, CuInSe₂, Cu(In,Ga)Se₂, CuGaSe₂, andAgInS₂ are examples of ternary chalcopyrite materials. It should benoted that ternary chalcopyrites include materials having multipleand/or different atoms from each of three Groups of the periodic table.For example, CuInSSe is a ternary chalcopyrite because it has Cu (GroupIB), In (Group IIIA), and S and Se (both from Group VIA). In addition,materials of the form (Cu:Ag)(In:Ga)(S:Se), having various ratios of therespectively grouped atoms are all ternary chalcopyrites (Cu and Ag bothare in Group IB, In and Ga both are in Group IIIA, S and Se both are inGroup VIA).

As used herein, the terms “single source precursor” and “SSP” mean andinclude any substance (e.g., a molecule or complex) that comprises allof the necessary atomic elements, in the appropriate stoichiometricratios, necessary to form a chalcogenide material (e.g., a ternarychalcopyrite material). Single source precursors may comprise so-calledorganometallic substances. As non-limiting examples, single sourceprecursors include molecules or complexes having the empirical formula[L₂N(μ-ER)₂M(ER)₂] (or L₂NM(ER)₄), wherein L is a Lewis base that iscoordinated to N by a dative bond, each N is individually selected fromGroup IB atoms, each M is individually selected from Group IIIA atoms,each E is individually selected from Group VIA atoms, and each R isindividually selected from the group consisting of alkyl, aryl, vinyl,(per)fluoro alkyl, (per)fluoro aryl, silane, and carbamato groups. Asseven particular non-limiting examples, single source precursors include(Ph₃P)₂Cu(μ-SEt)₂In(SEt)₂, (Ph₃P)₂Cu(μ-SEt)₂Ga(SEt)₂,(Ph₃P)₂Cu(μ-SEt)₂Al(SEt)₂, (Ph₃P)₂Ag(μ-SEt)₂In(SEt)₂,(Ph₃P)₂Ag(μ-SEt)₂Ga(SEt)₂, (Ph₃P)₂Ag(μ-SEt)₂Al(SEt)₂, and{(Ph₃P)₂Cu(μ-Cl)₂InCl₂}₂.

By way of example and not limitation, the following are examples ofcopper-indium SSPs:[bis(ethanethiolato)indium]bis[μ-(ethanethiolato)]bis(triisobutylphosphine)-copper;[bis(ethanethiolato)indium]bis[μ-(ethanethiolato)]bis(trihexylphosphine)-copper;[bis(ethanethiolato)indium]bis[μ-(ethanethiolato)]bis(triphenylphosphine)-copper;[bis(ethanethiolato)indium]bis[μ-(ethanethiolato)]bis(perfluorotriphenylphosphine)-copper;[bis(propanethiolato)indium]bis[μ-(propanethiolato)]bis(triisobutylphosphine)-copper;[bis(propanethiolato)indium]bis[μ-(propanethiolato)]bis(trihexylphosphine)-copper;[bis(propanethiolato)indium]bis[μ-(propanethiolato)]bis(triphenylphosphine)-copper;[bis(propanethiolato)indium]bis[μ-(propanethiolato)]bis(perfluorotriphenylphosphine)-copper;[bis(hexanethiolato)indium]bis[μ-(propanethiolato)]bis(triisobutylphosphine)-copper;[bis(hexanethiolato)indium]bis[μ-(propanethiolato)]bis(trihexylphosphine)-copper;[bis(hexanethiolato)indium]bis[μ-(propanethiolato)]bis(triphenylphosphine)-copper;[bis(hexanethiolato)indium]bis[μ-(propanethiolato)]bis(perfluorotriphenylphosphine)-copper;[bis(4-trifluoromethyl-thiophenolato)indium]bis[μ-(4-trifluoromethylthiophenolato)]bis(triisobutylphosphine)-copper;[bis(4-trifluoromethyl-thiophenolato)indium]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(trihexylphosphine)-copper;[bis(4-trifluoromethyl-thiophenolato)indium]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(triphenylphosphine)-copper;[bis(4-trifluoromethyl-thiophenolato)indium]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(perfluorotriphenylphosphine)-copper;[bis(3,5-bis(trifluoromethyl)-thiophenolato)indium]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(triisobutylphosphine)-copper;[bis(3,5-bis(trifluoromethyl)-thiophenolato)indium]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(trihexylphosphine)-copper;[bis(3,5-bis(trifluoromethyl)-thiophenolato)indium]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(triphenylphosphine)-copper;[bis(3,5-bis(trifluoromethyl)-thiophenolato)indium]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(perfluorotriphenylphosphine)-copper;[bis(thiophenolato)indium]bis[μ-(thiophenolato)]bis(triisobutylphosphine)-copper;[bis(thiophenolato)indium]bis[μ-(thiophenolato)]bis(trihexylphosphine)-copper;[bis(thiophenolato)indium]bis[μ-(thiophenolato)]bis(triphenylphosphine)-copper;[bis(thiophenolato)indium]bis[μ-(thiophenolato)]bis(perfluorotriphenylphosphine)-copper;[bis(α-toluenethiolato)indium]bis[μ-(α-toluenethiolato)]bis(triisobutylphosphine)-copper;[bis(α-toluenethiolato)indium]bis[μ-(α-toluenethiolato)]bis(trihexylphosphine)-copper;[bis(α-toluenethiolato)indium]bis[μ-(α-toluenethiolato)]bis(triphenylphosphine)-copper;[bis(α-toluenethiolato)indium]bis[μ-(α-toluenethiolato)]bis(perfluorotriphenylphosphine)-copper;[bis(pentafluorothiophenolato)indium]bis[μ-(pentafluorothiophenolato)]bis(triisobutylphosphine)-copper;[bis(pentafluorothiophenolato)indium]bis[m(pentafluorothiophenolato)]bis(trihexylphosphine)-copper;[bis(pentafluorothiophenolato)indium]bis[μ-(pentafluorothiophenolato)]bis(triphenylphosphine)-copper;[bis(pentafluorothiophenolato)indium]bis[μ-(pentafluorothiophenolato)]bis(perfluorotriphenylphosphine)-copper;[bis(thiobenzoato)indium]bis[μ-(thiobenzoato)]bis(triisobutylphosphine)-copper;[bis(thiobenzoato)indium]bis[μ-(thiobenzoato)]bis(trihexylphosphine)-copper;[bis(thiobenzoato)indium]bis[μ-(thiobenzoato)]bis(triphenylphosphine)-copper;[bis(thiobenzoato)indium]bis[μ-(thiobenzoato)]bis(perfluorotriphenylphosphine)-copper;[bis(thiobenzoato)indium]bis[μ-(thiobenzoato)]bis[ethylenebis(diphenylphosphine)]-copper;[bis(thiobenzoato)indium]bis[μ-(thiobenzoato)]bis[bis(2-diphenylphosphinophenyl)ether]-copper;[bis(thiobenzoato)indium]bis[μ-(thiobenzoato)]bis(trimethylphosphine)-copper;[bis(ethanethiolato)indium]bis[μ-(ethanethiolato)]bis[ethylenebis(diphenylphosphine)]-copper;[bis(ethanethiolato)indium]bis[μ-(ethanethiolato)]bis[bis(2-diphenylphosphinophenyl)ether]-copper;[bis(ethanethiolato)indium]bis[μ-(thiophenolato)]bis(triphenylphosphine)-copper;and[bis(ethanethiolato)indium]bis[μ-(ethanethiolato)]bis(trimethylphosphine)-copper.

By way of example and not limitation, the following are examples ofcopper-gallium SSPs:[bis(ethanethiolato)gallium]bis[μ-(ethanethiolato)]bis(triisobutylphosphine)-copper;[bis(ethanethiolato)gallium]bis[μ-(ethanethiolato)]bis(trihexylphosphine)-copper;[bis(ethanethiolato)gallium]bis[μ-(ethanethiolato)]bis(triphenylphosphine)-copper;[bis(ethanethiolato)gallium]bis[μ-(ethanethiolato)]bis(perfluorotriphenylphosphine)-copper;[bis(propanethiolato)gallium]bis[μ-(propanethiolato)]bis(triisobutylphosphine)-copper;[bis(propanethiolato)gallium]bis[μ-(propanethiolato)]bis(trihexylphosphine)-copper;[bis(propanethiolato)gallium]bis[μ-(propanethiolato)]bis(triphenylphosphine)-copper;[bis(propanethiolato)gallium]bis[μ-(propanethiolato)]bis(perfluorotriphenylphosphine)-copper;[bis(hexanethiolato)gallium]bis[μ-(propanethiolato)]bis(triisobutylphosphine)-copper;[bis(hexanethiolato)gallium]bis[μ-(propanethiolato)]bis(trihexylphosphine)-copper;[bis(hexanethiolato)gallium]bis[μ-(propanethiolato)]bis(triphenylphosphine)-copper;[bis(hexanethiolato)gallium]bis[μ-(propanethiolato)]bis(perfluorotriphenylphosphine)-copper;[bis(4-trifluoromethyl-thiophenolato)gallium]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(triisobutylphosphine)-copper;[bis(4-trifluoromethyl-thiophenolato)gallium]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(trihexylphosphine)-copper;[bis(4-trifluoromethyl-thiophenolato)gallium]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(triphenylphosphine)-copper;[bis(4-trifluoromethyl-thiophenolato)gallium]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(perfluorotriphenylphosphine)-copper;[bis(3,5-bis(trifluoromethyl)-thiophenolato)gallium]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(triisobutylphosphine)-copper;[bis(3,5-bis(trifluoromethyl)-thiophenolato)gallium]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(trihexylphosphine)-copper;[bis(3,5-bis(trifluoromethyl)-thiophenolato)gallium]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(triphenylphosphine)-copper;[bis(3,5-bis(trifluoromethyl)-thiophenolato)gallium]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(perfluorotriphenylphosphine)-copper;[bis(thiophenolato)gallium]bis[μ-(thiophenolato)]bis(triisobutylphosphine)-copper;[bis(thiophenolato)gallium]bis[μ-(thiophenolato)]bis(trihexylphosphine)-copper;[bis(thiophenolato)gallium]bis[μ-(thiophenolato)]bis(triphenylphosphine)-copper;[bis(thiophenolato)gallium]bis[μ-(thiophenolato)]bis(perfluorotriphenylphosphine)-copper;[bis(α-toluenethiolato)gallium]bis[μ-(α-toluenethiolato)]bis(triisobutylphosphine)-copper;[bis(α-toluenethiolato)gallium]bis[μ-(α-toluenethiolato)]bis(trihexylphosphine)-copper;[bis(α-toluenethiolato)gallium]bis[μ-(α-toluenethiolato)]bis(triphenylphosphine)-copper;[bis(α-toluenethiolato)gallium]bis[μ-(α-toluenethiolato)]bis(perfluorotriphenylphosphine)-copper;[bis(pentafluorothiophenolato)gallium]bis[μ-(pentafluorothiophenolato)]bis(triisobutylphosphine)-copper;[bis(pentafluorothiophenolato)gallium]bis[μ-(pentafluorothiophenolato)]bis(trihexylphosphine)-copper;[bis(pentafluorothiophenolato)gallium]bis[μ-(pentafluorothiophenolato)]bis(triphenylphosphine)-copper;and [bis(pentafluorothiophenolato)gallium]bis[μ-(pentafluorothiophenolato)]bis(perfluorotriphenylphosphine)-copper.

By way of example and not limitation, the following are examples ofsilver-indium SSPs:[bis(ethanethiolato)indium]bis[μ-(ethanethiolato)]bis(triisobutylphosphine)-silver;[bis(ethanethiolato)indium]bis[μ-(ethanethiolato)]bis(trihexylphosphine)-silver;[bis(ethanethiolato)indium]bis[μ-(ethanethiolato)]bis(triphenylphosphine)-silver;[bis(ethanethiolato)indium]bis[μ-(ethanethiolato)]bis(perfluorotriphenylphosphine)-silver;[bis(propanethiolato)indium]bis[μ-(propanethiolato)]bis(triisobutylphosphine)-silver;[bis(propanethiolato)indium]bis[μ-(propanethiolato)]bis(trihexylphosphine)-silver;[bis(propanethiolato)indium]bis[μ-(propanethiolato)]bis(triphenylphosphine)-silver;[bis(propanethiolato)indium]bis[μ-(propanethiolato)]bis(perfluorotriphenylphosphine)-silver;[bis(hexanethiolato)indium]bis[μ-(propanethiolato)]bis(triisobutylphosphine)-silver;[bis(hexanethiolato)indium]bis[μ-(propanethiolato)]bis(trihexylphosphine)-silver;[bis(hexanethiolato)indium]bis[μ-(propanethiolato)]bis(triphenylphosphine)-silver;[bis(hexanethiolato)indium]bis[μ-(propanethiolato)]bis(perfluorotriphenylphosphine)-silver;[bis(4-trifluoromethyl-thiophenolato)indium]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(triisobutylphosphine)-silver;[bis(4-trifluoromethyl-thiophenolato)indium]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(trihexylphosphine)-silver;[bis(4-trifluoromethyl-thiophenolato)indium]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(triphenylphosphine)-silver;[bis(4-trifluoromethyl-thiophenolato)indium]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(perfluorotriphenylphosphine)-silver;[bis(3,5-bis(trifluoromethyl)-thiophenolato)indium]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(triisobutylphosphine)-silver;[bis(3,5-bis(trifluoromethyl)-thiophenolato)indium]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(trihexylphosphine)-silver;[bis(3,5-bis(trifluoromethyl)-thiophenolato)indium]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(triphenylphosphine)-silver;and[bis(3,5-bis(trifluoromethyl)-thiophenolato)indium]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(perfluorotriphenylphosphine)-silver.

By way of example and not limitation, the following are examples ofsilver-gallium SSPs:[bis(ethanethiolato)gallium]bis[μ-(ethanethiolato)]bis(triisobutylphosphine)-silver;[bis(ethanethiolato)gallium]bis[μ-(ethanethiolato)]bis(trihexylphosphine)-silver;[bis(ethanethiolato)gallium]bis[μ-(ethanethiolato)]bis(triphenylphosphine)-silver;[bis(ethanethiolato)gallium]bis[μ-(ethanethiolato)]bis(perfluorotriphenylphosphine)-silver;[bis(propanethiolato)gallium]bis[μ-(propanethiolato)]bis(triisobutylphosphine)-silver;[bis(propanethiolato)gallium]bis[μ-(propanethiolato)]bis(trihexylphosphine)-silver;[bis(propanethiolato)gallium]bis[μ-(propanethiolato)]bis(triphenylphosphine)-silver;[bis(propanethiolato)gallium]bis[μ-(propanethiolato)]bis(perfluorotriphenylphosphine)-silver;[bis(hexanethiolato)gallium]bis[μ-(propanethiolato)]bis(triisobutylphosphine)-silver;[bis(hexanethiolato)gallium]bis[μ-(propanethiolato)]bis(trihexylphosphine)-silver;[bis(hexanethiolato)gallium]bis[μ-(propanethiolato)]bis(triphenylphosphine)-silver;[bis(hexanethiolato)gallium]bis[μ-(propanethiolato)]bis(perfluorotriphenylphosphine)-silver;[bis(4-trifluoromethyl-thiophenolato)gallium]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(triisobutylphosphine)-silver;[bis(4-trifluoromethyl-thiophenolato)gallium]bis[m(4-trifluoromethyl-thiophenolato)]bis(trihexylphosphine)-silver;[bis(4-trifluoromethyl-thiophenolato)gallium]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(triphenylphosphine)-silver;[bis(4-trifluoromethyl-thiophenolato)gallium]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(perfluorotriphenylphosphine)-silver;[bis(3,5-bis(trifluoromethyl)-thiophenolato)gallium]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(triisobutylphosphine)-silver;[bis(3,5-bis(trifluoromethyl)-thiophenolato)gallium]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(trihexylphosphine)-silver;[bis(3,5-bis(trifluoromethyl)-thiophenolato)gallium]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(triphenylphosphine)-silver;[bis(3,5-bis(trifluoromethyl)-thiophenolato)gallium]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(perfluorotriphenylphosphine)-silver;[bis(thiophenolato)gallium]bis[μ-(thiophenolato)]bis(triisobutylphosphine)-silver;[bis(thiophenolato)gallium]bis[μ-(thiophenolato)]bis(trihexylphosphine)-silver;[bis(thiophenolato)gallium]bis[μ-(thiophenolato)]bis(triphenylphosphine)-silver;[bis(thiophenolato)gallium]bis[μ-(thiophenolato)]bis(perfluorotriphenylphosphine)-silver;[bis(α-toluenethiolato)gallium]bis[μ-(α-toluenethiolato)]bis(triisobutylphosphine)-silver;[bis(α-toluenethiolato)gallium]bis[μ-(α-toluenethiolato)]bis(trihexylphosphine)-silver;[bis(α-toluenethiolato)gallium]bis[μ-(α-toluenethiolato)]bis(triphenylphosphine)-silver;[bis(α-toluenethiolato)gallium]bis[μ-(α-toluenethiolato)]bis(perfluorotriphenylphosphine)-silver;[bis(pentafluorothiophenolato)gallium]bis[μ-(pentafluorothiophenolato)]bis(triisobutylphosphine)-silver;[bis(pentafluorothiophenolato)gallium]bis[μ-(pentafluorothiophenolato)]bis(trihexylphosphine)-silver;[bis(pentafluorothiophenolato)gallium]bis[μ-(pentafluorothiophenolato)]bis(triphenylphosphine)-silver;and [bis(pentafluorothiophenolato)gallium]bis[μ-(pentafluorothiophenolato)]bis(perfluorotriphenylphosphine)-silver.

By way of example and not limitation, the following are examples ofcopper-aluminum SSPs:[bis(ethanethiolato)aluminum]bis[μ-(ethanethiolato)]bis(triisobutylphosphine)-copper;[bis(ethanethiolato)aluminum]bis[μ-(ethanethiolato)]bis(trihexylphosphine)-copper;[bis(ethanethiolato)aluminum]bis[μ-(ethanethiolato)]bis(triphenylphosphine)-copper;[bis(ethanethiolato)aluminum]bis[μ-(ethanethiolato)]bis(perfluorotriphenylphosphine)-copper;[bis(propanethiolato)aluminum]bis[μ-(propanethiolato)]bis(triisobutylphosphine)-copper;[bis(propanethiolato)aluminum]bis[μ-(propanethiolato)]bis(trihexylphosphine)-copper;[bis(propanethiolato)aluminum]bis[μ-(propanethiolato)]bis(triphenylphosphine)-copper;[bis(propanethiolato)aluminum]bis[μ-(propanethiolato)]bis(perfluorotriphenylphosphine)-copper;[bis(hexanethiolato)aluminum]bis[μ-(propanethiolato)]bis(triisobutylphosphine)-copper;[bis(hexanethiolato)aluminum]bis[μ-(propanethiolato)]bis(trihexylphosphine)-copper;[bis(hexanethiolato)aluminum]bis[μ-(propanethiolato)]bis(triphenylphosphine)-copper;[bis(hexanethiolato)aluminum]bis[μ-(propanethiolato)]bis(perfluorotriphenylphosphine)-copper;[bis(4-trifluoromethyl-thiophenolato)aluminum]bis[μ-(4-trifluoromethylthiophenolato)]bis(triisobutylphosphine)-copper;[bis(4-trifluoromethyl-thiophenolato)aluminum]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(trihexylphosphine)-copper;[bis(4-trifluoromethyl-thiophenolato)aluminum]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(triphenylphosphine)-copper;[bis(4-trifluoromethyl-thiophenolato)aluminum]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(perfluorotriphenylphosphine)-copper;[bis(3,5-bis(trifluoromethyl)-thiophenolato)aluminum]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(triisobutylphosphine)-copper;[bis(3,5-bis(trifluoromethyl)-thiophenolato)aluminum]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(trihexylphosphine)-copper;[bis(3,5-bis(trifluoromethyl)-thiophenolato)aluminum]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(triphenylphosphine)-copper;[bis(3,5-bis(trifluoromethyl)-thiophenolato)aluminum]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(perfluorotriphenylphosphine)-copper;[bis(thiophenolato)aluminum]bis[μ-(thiophenolato)]bis(triisobutylphosphine)-copper;[bis(thiophenolato)aluminum]bis[μ-(thiophenolato)]bis(trihexylphosphine)-copper;[bis(thiophenolato)aluminum]bis[μ-(thiophenolato)]bis(triphenylphosphine)-copper;[bis(thiophenolato)aluminum]bis[μ-(thiophenolato)]bis(perfluorotriphenylphosphine)-copper;[bis(α-toluenethiolato)aluminum]bis[μ-(α-toluenethiolato)]bis(triisobutylphosphine)-copper;[bis(α-toluenethiolato)aluminum]bis[μ-(α-toluenethiolato)]bis(trihexylphosphine)-copper;[bis(α-toluenethiolato)aluminum]bis[μ-(α-toluenethiolato)]bis(triphenylphosphine)-copper;[bis(α-toluenethiolato)aluminum]bis[μ-(α-toluenethiolato)]bis(perfluorotriphenylphosphine)-copper;[bis(pentafluorothiophenolato)aluminum]bis[μ-(pentafluorothiophenolato)]bis(triisobutylphosphine)-copper;[bis(pentafluorothiophenolato)aluminum]bis[μ-(pentafluorothiophenolato)]bis(trihexylphosphine)-copper;[bis(pentafluorothiophenolato)aluminum]bis[μ-(pentafluorothiophenolato)]bis(triphenylphosphine)-copper;and[bis(pentafluorothiophenolato)aluminum]bis[μ-(pentafluorothiophenolato)]bis(perfluorotriphenylphosphine)-copper.

By way of example and not limitation, the following are examples ofsilver-aluminum SSPs:[bis(ethanethiolato)aluminum]bis[μ-(ethanethiolato)]bis(triisobutylphosphine)-silver;[bis(ethanethiolato)aluminum]bis[μ-(ethanethiolato)]bis(trihexylphosphine)-silver;[bis(ethanethiolato)aluminum]bis[μ-(ethanethiolato)]bis(triphenylphosphine)-silver;[bis(ethanethiolato)aluminum]bis[μ-(ethanethiolato)]bis(perfluorotriphenylphosphine)-silver;[bis(propanethiolato)aluminum]bis[μ-(propanethiolato)]bis(triisobutylphosphine)-silver;[bis(propanethiolato)aluminum]bis[μ-(propanethiolato)]bis(trihexylphosphine)-silver;[bis(propanethiolato)aluminum]bis[μ-(propanethiolato)]bis(triphenylphosphine)-silver;[bis(propanethiolato)aluminum]bis[μ-(propanethiolato)]bis(perfluorotriphenylphosphine)-silver;[bis(hexanethiolato)aluminum]bis[μ-(propanethiolato)]bis(triisobutylphosphine)-silver;[bis(hexanethiolato)aluminum]bis[μ-(propanethiolato)]bis(trihexylphosphine)-silver;[bis(hexanethiolato)aluminum]bis[μ-(propanethiolato)]bis(triphenylphosphine)-silver;[bis(hexanethiolato)aluminum]bis[μ-(propanethiolato)]bis(perfluorotriphenylphosphine)-silver;[bis(4-trifluoromethyl-thiophenolato)aluminum]bis[i-(4-trifluoromethylthiophenolato)]bis(triisobutylphosphine)-silver;[bis(4-trifluoromethyl-thiophenolato)aluminum]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(trihexylphosphine)-silver;[bis(4-trifluoromethyl-thiophenolato)aluminum]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(triphenylphosphine)-silver;[bis(4-trifluoromethyl-thiophenolato)aluminum]bis[μ-(4-trifluoromethyl-thiophenolato)]bis(perfluorotriphenylphosphine)-silver;[bis(3,5-bis(trifluoromethyl)-thiophenolato)aluminum]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(triisobutylphosphine)-silver;[bis(3,5-bis(trifluoromethyl)-thiophenolato)aluminum]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(trihexylphosphine)-silver;[bis(3,5-bis(trifluoromethyl)-thiophenolato)aluminum]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(triphenylphosphine)-silver;[bis(3,5-bis(trifluoromethyl)-thiophenolato)aluminum]bis[μ-(3,5-bis(trifluoromethyl)-thiophenolato)]bis(perfluorotriphenylphosphine)-silver;[bis(thiophenolato)aluminum]bis[μ-(thiophenolato)]bis(triisobutylphosphine)-silver;[bis(thiophenolato)aluminum]bis[μ-(thiophenolato)]bis(trihexylphosphine)-silver;[bis(thiophenolato)aluminum]bis[μ-(thiophenolato)]bis(triphenylphosphine)-silver;[bis(thiophenolato)aluminum]bis[μ-(thiophenolato)]bis(perfluorotriphenylphosphine)-silver;[bis(α-toluenethiolato)aluminum]bis[μ-(α-toluenethiolato)]bis(triisobutylphosphine)-silver;[bis(α-toluenethiolato)aluminum]bis[μ-(α-toluenethiolato)]bis(trihexylphosphine)-silver;[bis(α-toluenethiolato)aluminum]bis[μ-(α-toluenethiolato)]bis(triphenylphosphine)-silver;[bis(α-toluenethiolato)aluminum]bis[μ-(α-toluenethiolato)]bis(perfluorotriphenylphosphine)-silver;[bis(pentafluorothiophenolato)aluminum]bis[μ-(pentafluorothiophenolato)]bis(triisobutylphosphine)-silver;[bis(pentafluorothiophenolato)aluminum]bis[μ-(pentafluorothiophenolato)]bis(trihexylphosphine)-silver;[bis(pentafluorothiophenolato)aluminum]bis[μ-(pentafluorothiophenolato)]bis(triphenylphosphine)-silver;and[bis(pentafluorothiophenolato)aluminum]bis[μ-(pentafluorothiophenolato)]bis(perfluorotriphenylphosphine)-silver.

The examples of SSPs set forth above are examples only, and those ofordinary skill in the art will understand that such examples may be usedto derive many other SSPs for use in forming chalcogenide materials suchas, for example, ternary chalcopyrite materials.

Embodiments of the present invention include methods of forming SSPs.The methods are believed to be generally faster, more versatile (may beused to form a wider variety of SSPs), and to exhibit improved yieldrelative to other methods known in the art.

An example of a reaction pathway in accordance with some embodiments ofthe present invention is represented by Reactions 1 through 3 below:

In some embodiments of the present invention, SSPs of the generalformula L₂N(μ-ER)₂M′(ER)₂ may be funned using a reaction pathway inaccordance with Reactions 1 through 3 below:

N—X+2L→L₂N—X  Reaction 1

L₂N—X+M′X₃→½{L₂N(μ-X)₂M′X₂}₂  Reaction 2

½{L₂N(μ-X)₂M′X₂}₂+4MER→L₂N(μ-ER)₂M′(ER)₂(+4MX)(SSP)  Reaction 3

wherein L is a Lewis base (that is coordinated to N by a dative bond),each N is individually selected from Group IB atoms, each M isindividually selected from Group IA atoms, each M′ is individuallyselected from Group IIIA atoms, each E is individually selected fromGroup VIA atoms, each X is individually selected from Group VIIA atomsor a nitrate group, and each R group is individually selected from thegroup consisting of alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoroaryl, silane, and carbamato groups. In accordance with some embodimentsof the present invention, the Lewis base L may comprise, for example, asubstituted phosphine of the general formula PR₃, wherein P is aphosphorous atom and each R is individually selected from the groupconsisting of alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl,silane, and carbamato groups. As a non-limiting example, the Lewis baseL may comprise a phosphine compound such as Ph₃P, wherein Ph is thephenyl group (a functional group comprising an aromatic cyclic ring ofthe formula C₆H₅ ⁻). In accordance with additional embodiments of thepresent invention, the Lewis base L may comprise, for example, asubstituted multidentate phosphine of the general formula R₂PAPR₂,wherein P is a phosphorous atom, each A is individually selected fromthe group consisting of alkyl, aryl, and vinyl, and each R isindividually selected from the group consisting of alkyl, aryl, vinyl,(per)fluoro alkyl, (per)fluoro aryl, silane, and carbamato groups. As anon-limiting example, the Lewis base L may comprise a phosphine compoundsuch as Ph₂PC₆H₄OC₆H₄PPh₂ (bis(2-diphenylphosphinophenyl)ether), whereinPh is the phenyl group (a functional group comprising an aromatic cyclicring of the formula C₆H₅ ⁻).

Reactions 1 through 3 above, when combined and balanced, result in thenet reaction N—X+2L+M′X₃+4MER→L₂N(μ-ER)₂M′(ER)₂(+4MX). The particularreaction pathway prescribed by Reactions 1 through 3 results in theformation of the intermediate products L₂N—X and ½{L₂N(μ-X)₂M′X₂}₂. Suchreaction pathways provide certain advantages over previously knownmethods of forming SSPs having the general formula L₂N(μ-ER)₂M′(ER)₂.

Referring to Reaction 1, a first reagent comprising L₂N—X (for use inReaction 2) may be formed by reacting a Lewis base (e.g., a substitutedphosphine (PR₃)) with a metal halide or nitride (N—X). The molar ratioof the Lewis base to the metal halide or nitride may be, for example,two (2) to one (1) (in other words, two molar equivalents of the Lewisbase and one molar equivalent of the metal halide or nitride may bereacted with one another in Reaction 1), although the particular molarratio may depend on the particular SSP to be formed.

Reaction 1 may be carried out in solution. For example, Reaction 1 maybe performed in anhydrous benzene (C₆H₆), in acetonitrile (CH₃CN), in amixture of more than one solvent, or in another suitable solvent. Theproduct of Reaction 1 may comprise a suspension in which the firstreagent comprising L₂N—X is present as a liquid or solid productsuspended in the solution. The suspension may be concentrated to yield aliquid or a solid product comprising the L₂N—X substance. Alternatively,the reaction may be conducted in a single pot reaction, wherein theL₂N—X substance is not concentrated.

Referring to Reaction 2, the intermediate product ½{L₂N(μ-X)₂M′X₂}₂ maybe formed by reacting the first reagent comprising L₂N—X with M′X₃. Themolar ratio of the L₂N—X reagent to the M′X₃ reagent may be, forexample, one (1) to one (1) (in other words, one molar equivalent of theL₂N—X reagent and one molar equivalent of the M′X₃ reagent may bereacted with one another in Reaction 2), although, again, the particularmolar ratio may depend on the particular SSP to be formed.

Reaction 2 also may be carried out in solution. For example, Reaction 2may be performed in the same benzene (C₆H₆) (or other solvent or solventmixture) used in Reaction 1 or another suitable solvent (i.e., a solventin which the L₂N—X reagent and/or the M′X₃ reagent is soluble). Theproduct of Reaction 2 may comprise a solution or a suspension comprisingthe intermediate product ½{L₂N(μ-X)₂M′X₂}₂.

Referring to Reaction 3, an SSP of the general formula L₂N(μ-ER)₂M′(ER)₂may be formed by reacting the intermediate product ½{L₂N(μ-X)₂M′X₂}₂ ofReaction 2 with the MER reagent. By way of example and not limitation,the MER reagent may be added to the solution or suspension that is theproduct of Reaction 2 and includes the intermediate product½{L₂N(μ-X)₂M′X₂}₂. The molar ratio of the MER reagent to the½{L₂N(μ-X)₂M′X₂}₂ reagent may be, for example, four (4) to one (1) (inother words, four molar equivalents of the MER reagent and one molarequivalent of the ½{L₂N(μ-X)₂M′X₂}₂ reagent may be reacted with oneanother in Reaction 3), although, again, the particular molar ratio maydepend on the particular SSP to be formed. It is noted that the R groupsin the four molar equivalents of the MER reagent may differ from oneanother, and may be individually selected from the group consisting ofalkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl, silane, andcarbamato groups. In other words, one molar equivalent of the MERreagent may comprise R¹, one molar equivalent of the MER reagent maycomprise R², one molar equivalent of the MER reagent may comprise R³,and one molar equivalent of the MER reagent may comprise R⁴, wherein R¹,R², R³, and R⁴ all differ from one another. In additional embodiments,less than four different R groups (e.g., one, two, or three), or morethan four different R groups may be employed in the MER reagent.Similarly, the E groups in the four molar equivalents of the MER reagentmay differ from one another, and may be individually selected from theGroup VIA atoms. In other words, one molar equivalent of the MER reagentmay comprise E¹, one molar equivalent of the MER reagent may compriseE², one molar equivalent of the MER reagent may comprise E³, and onemolar equivalent of the MER reagent may comprise E⁴, wherein E¹, E², E³,and E⁴ all differ from one another. In additional embodiments, less thanfour different E groups (e.g., one, two, or three), or more than fourdifferent E groups may be employed in the MER reagent.

Reaction 3 also may be carried out in solution. For example, Reaction 3may be performed in the same in the same benzene (C₆H₆) (or othersolvent or solvent mixture) used in Reaction 2 or another suitablesolvent, after carrying out Reaction 2, such that the solution includesthe intermediate product and reagent ½{L₂N(μ-X)₂M′X₂}₂. The product ofReaction 3 may comprise a suspension in which the SSP of the generalformula L₂N(μ-ER)₂M′(ER)₂ is present as a liquid or solid productdissolved or suspended in the solution. The by-product may be filtered,and the filtrate may be concentrated to isolate the SSP. The SSP maycomprise a liquid or solid product, and the solid SSP may bere-crystallized as desirable in preparation for utilizing the SSP toform a chalcogenide material (e.g., a ternary chalcopyrite material).

In accordance with some embodiments of the present invention, SSPs ofthe general formula L₂N(μ-E¹R¹)(μ-E²R²)M′(E²R²)₂ (SSP) orL₂N(μ-E²R²)₂M′(E²R²)(E¹R¹) (SSP) may be formed using reaction pathwaysin accordance with additional embodiments of the present inventionrepresented by Reaction 1 (which is the same as above and repeated belowfor convenience) and Reactions 4 through 6 below:

N—X+2L→L₂N—X  Reaction 1

L₂N—X+ME¹R¹→L₂N-E¹R¹(+MX)  Reaction 4

M′X₃ +nME²R²→M′(E²R²)_(n)(+nMX)  Reaction 5

L₂N-E′R′+M′(E²R²)_(n)→L₂N(μ-E¹R¹)(μ-E²R²)M′(E²R²)₂(SSP) orL₂N(μ-E²R²)₂M′(E²R²)(E¹R¹)(SSP)  Reaction 6

wherein L is a Lewis base (that is coordinated to N by a dative bond),each N is individually selected from Group IB atoms, each M isindividually selected from Group IA atoms, each M′ is individuallyselected from Group IIIA atoms, each E¹ and E² is individually selectedfrom Group VIA atoms (E¹ and E² may be same or different), each X isindividually selected from Group VIIA atoms or a nitrate group, n is anynumber (e.g., an integer) from one (1) to three (3), and each R¹ and R²group is individually selected from the group consisting of alkyl, aryl,vinyl, (per)fluoro alkyl, (per)fluoro aryl, silane, and carbamatogroups, wherein at least one E¹ differs from at least one E² and/or atleast one R¹ differs from at least one R². In some embodiments, each E¹may differ from each E². In some embodiments, each R¹ may differ fromeach R².

Reaction 1 may be carried out as previously described herein. Referringto Reaction 4, the intermediate product L₂N-E¹R¹ may be formed byreacting the L₂N—X (obtained by Reaction 1) with ME¹R¹. The molar ratioof the L₂N—X reagent to the ME¹R¹ reagent may be, for example, one (1)to one (1) (in other words, one molar equivalent of the L₂N—X reagentand one molar equivalent of the ME¹R¹ reagent may be reacted with oneanother in Reaction 4), although, again, the particular molar ratio maydepend on the particular SSP to be formed.

Reaction 4 also may be carried out in solution. For example, Reaction 4may be performed in the same benzene (C₆H₆) or other solution used inReaction 1, or in another suitable solvent (i.e., a solvent in which theL₂N—X reagent and/or the ME¹R¹ reagent is soluble). The product ofReaction 4 may comprise a solution or a suspension comprising theintermediate product L₂N-E¹R¹.

Referring to Reaction 5, the intermediate product M′(E²R²)_(n) may beformed by reacting M′X₃ with ME²R². The molar ratio of the M′X₃ reagentto the ME²R² reagent may be, for example, one (1) to three (3) (in otherwords, one molar equivalent of the M′X₃ reagent and three molarequivalents of the ME²R² reagent may be reacted with one another inReaction 5), although, again, the particular molar ratio may depend onthe particular SSP to be formed.

Reaction 5 also may be carried out in solution. For example, Reaction 5may be performed in the same benzene (C₆H₆) or other solution (i.e., asolvent in which the M′X₃ reagent and/or the ME²R² reagent is soluble).The product of Reaction 5 may comprise a solution or a suspensioncomprising the intermediate products M′(E²R²)_(n). It is noted that theR² groups in the four molar equivalents of the ME²R² reagent may beindividually selected from the group consisting of alkyl, aryl, vinyl,(per)fluoro alkyl, (per)fluoro aryl, silane, and carbamato groups. Thus,each of the R² groups may be the same or they may differ from oneanother. Similarly, the E² groups in the four molar equivalents of theME²R² reagent may be individually selected from the Group VIA atoms,and, thus, may be the same or they may differ from one another.

Referring to Reaction 6, an SSP of the general formulaL₂N(μ-E¹R¹)(μ-E²R²)M′(E²R²)₂ or L₂N(μ-E²R²)₂M′(E¹R¹)(E²R²) may be formedby reacting the intermediate product L₂N-E¹R¹ of Reaction 4 with theintermediate product M′(E²R²) of Reaction 5. By way of example and notlimitation, the intermediate product M′(E²R²)_(n) may be added to thesolution or suspension that is the product of Reaction 4 and includesthe intermediate product L₂N-E¹R¹. The molar ratio of the L₂N-E¹R′reagent to the M′(E²R²)_(n) reagent may be, for example, one (1) to one(1) (in other words, one molar equivalent of the L₂N-E¹R′ reagent andone molar equivalent of the M′(E²R²)_(n) reagent may be reacted with oneanother in Reaction 6), although, again, the particular molar ratio maydepend on the particular SSP to be formed.

Reaction 6 also may be carried out in solution. For example, Reaction 6may be performed in the same benzene (C₆H₆) or other solution used inReaction 5, after carrying out Reaction 5, such that the solutionincludes the intermediate product and reagent M′(E²R²). The product ofReaction 6 may comprise a suspension in which the SSP of the generalformula L₂N(μ-E¹R¹)(μ-E²R²)M′(E²R²)₂ or L₂N(μ-E²R²)₂M′(E¹R¹)(E²R²) ispresent as a liquid or solid dissolved or suspended in the solution. Theby-product may be filtered, and the filtrate may be concentrated toisolate the SSP. The SSP may comprise a liquid or solid product, and thesolid SSP may be re-crystallized as desirable in preparation forutilizing the SSP to form a chalcogenide material (e.g., a ternarychalcopyrite material).

In accordance some embodiments of the present invention, SSPs of thegeneral formula L₂N(μ-ER¹)(μ-ER²)M′(ER³)(ER⁴) may be formed usingReactions 1 and 4 (which are the same as above and repeated below forconvenience) and Reactions 7 through 10 below:

N—X+2L→L₂N—X  Reaction 1

L₂N—X+MER¹→L₂N-ER¹(+MX)  Reaction 4

L₂N-ER¹+M′X₃→L₂N(μ-ER¹)(μ-X)M′X₂  Reaction 7

L₂N(μ-ER¹)(μ-X)M′X₂+MER²→L₂N(μ-ER¹)(μ-ER²)M′X₂(+MX)  Reaction 8

L₂N(μ-ER¹)(μ-ER²)M′X₂+MER³→L₂N(μ-ER¹)(μ-ER²)M′(ER³)X(+MX)  Reaction 9

L₂N(μ-ER¹)(μ-ER²)M′(ER³)X+MER⁴→L₂N(μ-ER¹)(μ-ER²)M′(ER³)(ER⁴)(+MX)(SSP)  Reaction10

wherein L is a Lewis base that is coordinated to N by a dative bond,each N is individually selected from Group IB atoms, each M isindividually selected from Group IA atoms, each M′ is individuallyselected from Group IIIA atoms, each E is individually selected fromGroup VIA atoms, each X is individually selected from Group VIIA atomsor a nitrate group, each R¹, R², R³, and R⁴ group is individuallyselected from the group consisting of alkyl, aryl, vinyl, (per)fluoroalkyl, (per)fluoro aryl, silane, and carbamato groups, and R¹, R², R³,R⁴ are different from one another. The E groups in the MER¹, MER², MER³,and MER⁴ reagents may be the same or they may be different from oneanother. In other words, the MER¹ reagent may comprise E¹, the MER²reagent may comprise E², the MER³ reagent may comprise E³, and the MER⁴reagent may comprise E⁴, wherein E¹, E², E³, and E⁴ all differ from oneanother. In additional embodiments, less than four different E groups(e.g., one, two, or three), or more than four different E groups may beemployed in the MEW, MER², MER³, and MER⁴ reagents.

Reactions 1 and 4 may be carried out as previously described herein.

Referring to Reaction 7, the intermediate product L₂N(μ-ER¹)(μ-X)M′X₂(which may be an SSP) may be formed by reacting the L₂N-ER¹ (obtained byReaction 4) with M′X₃. The molar ratio of the L₂N-ER¹ reagent to theM′X₃ reagent may be, for example, one (1) to one (1) (in other words,one molar equivalent of the M′X₃ reagent and one molar equivalent of theL₂N-ER¹ reagent may be reacted with one another in Reaction 7). Reaction7 may be carried out in a solution such as benzene (C₆H₆) or in anothersuitable solvent or mixture of solvents. The product of Reaction 7 maycomprise a solution or a suspension comprising the intermediate SSPproduct L₂N(μ-ER¹)(μ-X)M′X₂.

Referring to Reaction 8, the intermediate SSP productL₂N(μ-ER¹)(μ-ER²)M′X₂ may be formed by reacting one (1) molar equivalentof MER² with the intermediate SSP product L₂N(μ-ER¹)(μ-X)M′X₂ ofReaction 7. As shown in Reaction 9, the intermediate SSP productL₂N(μ-ER¹)(μ-ER²)M′(ER³)X may be formed by reacting one (1) molarequivalent of MER³ with one (1) molar equivalent of the SSP intermediateproduct L₂N(μ-ER¹)(μ-ER²)M′X₂ obtained by Reaction 8. Similarly, asshown in Reaction 10, a final SSP product of the general formulaL₂N(μ-ER¹)(μ-ER²)M′(ER³)(ER⁴) may be formed by reacting one (1) molarequivalent of MER⁴ with one (1) molar equivalent of the SSP intermediateproduct L₂N(μ-ER¹)(μ-ER²)M′(ER³)X obtained by Reaction 9. The product ofReaction 10 may comprise a suspension in which an SSP of the generalformula L₂N(μ-ER¹)(μ-ER²)M′(ER³)(ER⁴) is present as a liquid or soliddissolved or suspended in the solution. It is noted that the variousgroups may not be added to the particular positions of the SSP in theorder represented above, and, thus, the ER¹, ER², ER³, and ER⁴ groupsmay be in any position in the SSP. The by-product may be filtered, andthe filtrate may be concentrated to isolate the SSP. The SSP maycomprise a liquid or solid product, and the solid SSP may bere-crystallized as desirable in preparation for utilizing the SSP toform a chalcogenide material (e.g., a ternary chalcopyrite material).

In accordance with additional embodiments of the present invention,after forming SSPs as previously described herein, the composition ofthe SSPs may be tailored by carrying out one or more additionalreactions (e.g., substitution reactions) with the SSPs, as describedbelow. For example, after forming a first SSP(SSP¹), a second, differentSSP(SSP²) of the general formula L₂N(μ-E¹R¹)(μ-E²R²)M′(E³R³)(E⁴R⁴) maybe formed from the first SSP¹ in accordance with Reaction 11 below:

SSP¹ +nHE¹R¹ +mHE²R² +oHE³R³+pHE⁴R⁴→L₂N(μ-E¹R¹)(μ-E²R²)M′(E³R³)(E⁴R⁴)(SSP2)  Reaction 11

wherein each of n, m, o, and p is any number between zero (0) and four(4), the sum of n, m, o, and p is four (4), L is a Lewis base that iscoordinated to N by a dative bond, each N is individually selected fromGroup IB atoms, each M′ is individually selected from Group IIIA atoms,each of E¹, E², E³, and E⁴ is individually selected from Group VIAatoms, each of R¹, R², R³, and R⁴ is individually selected from thegroup consisting of alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoroaryl, silane, and carbamato groups. In Reaction 11, R¹, R², R³, and R⁴may be the same or different from one another, and E¹, E², E³, and E⁴may be the same or different from one another.

As one non-limiting example, after forming an SSP of the general formulaL₂N(μ-ER)₂M′(ER)₂ using Reactions 1 through 3, as previously described,a different SSP of the general formula L₂N(μ-E¹R¹)₂M′(E¹R¹)₂ may beformed from the SSP in accordance with Reaction 11 by reacting four (4)molar equivalents of HE¹R¹ with one (1) molar equivalent of theL₂N(μ-E¹R¹)₂M′(E¹R¹)₂ SSP. As another non-limiting example, afterforming an SSP of the general formula L₂N(μ-E¹R¹)(μ-E²R²)M′(E²R²)₂ usingReactions 1, 4, 5, and 6, as previously described, a different SSP ofthe general formula L₂N(μ-E³R³)₂M′(E³R³)₂ may be formed from the SSP inaccordance with Reaction 11 by reacting four (4) molar equivalents ofHE³R³ with one (1) molar equivalent of theL₂N(μ-E¹R¹)(μ-E²R²)M′(E²R²)₂)SSP. As yet another non-limiting example,after forming an SSP of the general formulaL₂N(μ-ER¹)(μ-ER²)M′(ER³)(ER⁴) using Reactions 1, 4, and 7 through 10, aspreviously described, a different SSP of the general formulaL₂N(μ-E²R⁵)₂M′(E²R⁵)₂ may be formed from the SSP in accordance withReaction 11 by reacting four (4) molar equivalents of HE²R⁵ with one (1)molar equivalent of the L₂N(μ-ER¹)(μ-ER²)M′(ER³)(ER⁴) SSP.

Reaction 11 also may be carried out in solution. For example, Reaction11 may be performed in benzene (C₆H₆) or another suitable solvent orsolvent mixture. The product of Reaction 11 may comprise a suspension inwhich the SSP product is present as liquid or solid matter dissolved orsuspended in the solution. The by-product may be filtered, and thefiltrate may be concentrated to isolate the SSP product. The SSP productmay comprise a liquid or solid product, and the solid SSP may bere-crystallized as desirable in preparation for utilizing the SSP toform a chalcogenide material (e.g., a ternary chalcopyrite material).

The reaction mechanisms described hereinabove with reference toReactions 1 through 11 may be used to form a wide variety of SSPs. Forexample, different species of the L₂N—X reagent (Reaction 2) and theME¹R¹ reagent (Reaction 3) may be used to place different R¹ groups onthe SSPs, different E¹ groups on the SSPs, or different L groups on theSSPs, and different species of the L₂N—X reagent, the M′X₃ reagent, andthe ME¹R¹ reagent may be used in selected ratios to tailor the identityand concentration of the N, M′, and E atoms in the SSPs. Fournon-limiting examples of embodiments of the present invention are setforth below to illustrate the versatility in forming SSPs in accordancewith embodiments of the present invention. Embodiments of the presentinvention, however, are not to be limited to methods of forming thespecific SSPs aimed in the examples below, or to methods employing theparticular reagents employed in the examples below.

Example 1

The SSP (Ph₃P)₂Cu(μ-SEt)₂In(SEt)₂ may be formed as follows.

Two (2) molar equivalents of Ph₃P (42.000 grams, 160.13 millimoles) maybe added to a mixture of two hundred forty (240) milliliters (mL) ofanhydrous benzene (C₆H₆) and two hundred forty (240) milliliters (mL) ofanhydrous tetrahydrofuran ((CH₂)₄O, THF) to form a first solution, whichmay be stirred. One (1) molar equivalent of anhydrous Cu(I)Cl (7.9260grams, 80.064 millimoles) may be added to the stirring first solution toform a first white suspension including the intermediate product(Ph₃P)₂Cu—Cl. The first suspension may be concentrated to form a solidproduct or kept to continue the reaction as a one pot reaction, which isreferred to herein as “Mixture A.”

A second solution may be formed by adding 1.4770 molar equivalents of KH(40.000 grams, 299.18 millimoles, collected from thirty (30) weightpercent dispersion in mineral oil and washed several times with benzene)to about 100 mL of benzene. One (1) molar equivalent of EtSH (15.000 mL,202.56 millimoles) (Et is the ethyl group) may be added to the secondsolution and stirred for a few minutes. The EtSH and the KH react withone another to form KSEt. The resulting product that includes the KSEt(which may comprise a solution or a solid product comprising the KSEtformed by drying a solution) is referred to herein as “Mixture B.”

A “Mixture C” may also be formed by adding one (1) molar equivalent ofNa metal (34.000 grams, 1478.9 millimoles, collected from mineral oiland washed several times with diethyl ether) to about 500 mL of diethylether. One (1) molar equivalent of EtSH (109.52 mL, 1478.9 millimoles)may be added to the second solution and stirred for twelve (12) hours atforty (40) degrees Celsius (° C.). The EtSH and the Na metal react withone another to form NaSEt. The resulting product that includes the NaSEt(which may comprise a solution or a solid product comprising the NaSEtformed by drying a solution) is Mixture C.

If the reaction is a one pot reaction, one (1) molar equivalent ofanhydrous InCl₃ (17.709 grams, 80.064 millimoles) may be added toMixture A, after which this third solution may be stirred for aboutsixty (60) minutes at eighty (80) degrees Celsius (° C.). The resultingmixture may comprise a fourth solution. This solution may comprise theintermediate product {(Ph₃P)₂Cu(μ-Cl)₂InCl₂}₂, a computer generatedgraphical representation of which is illustrated in FIG. 1. As shown inFIG. 1, this intermediate product comprises an eight (8) member ringstructure defined by two (2) copper atoms, two (2) indium atoms, andfour (4) chlorine atoms.

Four (4) molar equivalents of NaSEt (26.940 grams, 320.26 millimoles) orKSEt (32.100 grams, 320.26 millimoles) provided by Mixture B or C,respectively, may be added to the fourth solution and stirred for anadditional twelve (12) hours at eighty (80)° C.

In some embodiments, however, less than four (4) molar equivalents ofthe NaSEt or KSEt may initially be added to the fourth solution.Fractions of the four (4) molar equivalents may be added sequentially toattain various intermediate products. For example, one (1) molarequivalent of the NaSEt or KSEt may initially be added to the fourthsolution to form an intermediate product, the exact nature of which isnot known, but is currently believed to be the (Ph₃P)₂Cu(μ-SEt)InCl₃species shown in the computer generated graphical representation of FIG.2. A second molar equivalent of the NaSEt or KSEt may be added to thefourth solution to form another intermediate product, the exact natureof which is not known, but is currently believed to be the(Ph₃P)₂Cu(μ-SEt)₂InCl₂ species shown in the computer generated graphicalrepresentation of FIG. 3. Similarly, a third molar equivalent of theNaSEt or KSEt may then be added to the fourth solution to form anotherintermediate product, the exact nature of which is not known, but iscurrently believed to be the (Ph₃P)₂Cu(μ-SEt)₂In(SEt)Cl species shown inthe computer generated graphical representation of FIG. 4. Finally, afourth molar equivalent of the NaSEt may be added to the fourth solutionto form the final SSP product (Ph₃P)₂Cu(μ-SEt)₂In(SEt)₂, which is shownin the computer generated graphical representation of FIG. 5.

After all four (4) molar equivalents of the NaSEt or KSEt provided byMixture B or C, respectively, have been added to the fourth solution,the solution may be stirred for an additional twelve (12) hours ateighty degrees Celsius (80° C.). After stirring, the resulting mixturemay comprise a suspension that includes a solution with particles of theSSP (Ph₃P)₂Cu(μ-SEt)₂In(SEt)₂ suspended therein. The SSP may be isolatedby filtering of by-product, and the filtrate may be concentrated asnecessary or desirable. Optionally, the isolated SSP may bere-crystallized in preparation for using the SSP to form the ternarychalcopyrite material CuInS₂.

It will be apparent from the above description that, in additionalembodiments, instead of using the same reagent (e.g., NaSEt) in each ofthe sequential additions to the reaction mixture, different reagentsincluding different moieties (other than ethyl groups) may be added tothe fourth solution to substitute different, selected moieties into theresulting SSP product at different selected locations within thestructure of the SSP molecule or complex.

Example 2

The SSP (Ph₃P)₂Cu(μ-SBn)(μ-SEt)Ga(SEt)₂ may be formed as follows.

The intermediate product (Ph₃P)₂Cu—Cl is formed as described in Example1 above (and repeated below for convenience). Two (2) molar equivalentsof Ph₃P (42.000 grams, 160.13 millimoles) may be added to mixture of twohundred forty (240) milliliters (mL) of anhydrous benzene (C₆H₆) and twohundred forty (240) milliliters (mL) of anhydrous tetrahydrofuran((CH₂)₄O, THF) to form a first solution, which may be stirred. One (1)molar equivalent of anhydrous Cu(I)Cl (7.9260 grams, 80.064 millimoles)may be added to the stirring first solution to form a first whitesuspension including the intermediate product (Ph₃P)₂Cu—Cl. The firstsuspension may be concentrated to form a solid product or kept tocontinue the reaction, which is referred to herein as “Mixture A.”

A second solution (which is the same as above and repeated below forconvenience) may be formed by adding one (1) molar equivalent of Nametal (34.000 grams, 1478.9 millimoles, collected from mineral oil andwashed several times with diethyl ether) to about 500 mL of diethylether. One (1) molar equivalent of EtSH (109.52 mL, 1478.9 millimoles)may be added to the second solution and stirred for twelve (12) hours atforty (40) degrees Celsius (° C.). The EtSH and the Na metal react withone another to form NaSEt. The resulting product that includes the NaSEt(which may comprise a solution or a solid product comprising the NaSEtformed by drying a solution) is referred to herein as “Mixture B.”

A third solution may be formed by adding one (1) molar equivalent of Nametal (10.000 grams, 434.97 millimoles, collected from mineral oil andwashed several times with diethyl ether) to about 200 mL of diethylether. One (1) molar equivalent of C₆H₅CH₂SH (HSBn, 51.066 mL, 434.97millimoles) may be added to the third solution and stirred for twelve(12) hours at 40° C. The C₆H₅CH₂SH and the Na metal react with oneanother to form NaSCH₂C₆H₅ (NaSBn). The resulting product that includesthe NaSBn (which may comprise a solution or a solid product comprisingthe NaSBn formed by drying a solution) is referred to herein as “MixtureC.”

A fourth solution may be Ruined by adding one (1) molar equivalent of(Ph₃P)₂Cu—Cl (49.926 grams, 80.064 millimoles) provided by Mixture A toabout 200 mL of benzene. One (1) molar equivalent of NaSBn (8.1840grams, 80.064 millimoles) provided by Mixture C may be added to thefourth solution and stirred for twelve (12) hours. The (Ph₃P)₂Cu—Cl andthe NaSBn react with one another to form (Ph₃P)₂CuSBn. The resultingmixture may comprise a fourth solution. This solution may comprise theintermediate product (Ph₃P)₂CuSBn (which may comprise a solution or asolid product comprising the (Ph₃P)₂CuSBn formed by drying a solution)is referred to herein as “Mixture D.”

A fifth solution may be formed by adding three (3) molar equivalents ofNaSEt (20.205 grams, 240.192 millimoles) provided by Mixture B to about200 mL of benzene. One (1) molar equivalent of anhydrous GaCl₃ (14.098grams, 80.064 millimoles) may be added to this fifth solution, afterwhich the fifth solution may be stirred for about sixty (60) minutes ateighty (80)° C. The resulting mixture may comprise a fifth solution.This solution may comprise the intermediate product Ga(SEt)₃ (which maycomprise a solution or a solid product comprising the Ga(SEt)₃ formed bydrying a solution).

One (1) molar equivalent of (Ph₃P)₂CuSBn (56.950 grams, 80.064millimoles) provided by Mixture D may be added to the fifth solution andstirred for an additional twelve (12) hours at eighty (80)° C. Afterstirring, the resulting mixture may comprise a suspension that includesa solution with particles of the SSP (Ph₃P)₂Cu(μ-SBn)(μ-SEt)Ga(SEt)₂suspended therein. The SSP may be isolated by filtering of by-product,and the filtrate may be concentrated as necessary or desirable.Optionally, the isolated SSP may be re-crystallized in preparation forusing the SSP to form the ternary chalcopyrite material CuGaS₂.

In some embodiments, however, less than three (3) molar equivalents ofthe NaSEt may initially be added to the fifth solution. Fractions of thethree (3) molar equivalents may be added sequentially to attain variousintermediate products. For example, one (1) molar equivalent of theNaSEt may initially be added to the fifth solution to form anintermediate product GaSEtCl₂. A second molar equivalent of the NaSEtmay be added to the fifth solution to form another intermediate productGa(SEt)₂Cl. Finally, a third molar equivalent of the NaSEt may then beadded to the fifth solution to form another intermediate productGa(SEt)₃.

It will be apparent from the above description that, in additionalembodiments, instead of using the same reagent (e.g., NaSEt) in each ofthe sequential additions to the reaction mixture, different reagentsincluding different moieties (other than ethyl groups) may be added tothe fourth solution to substitute different, selected moieties into theresulting SSP product at different selected locations within thestructure of the SSP molecule or complex.

Example 3

The SSP (Ph₃P)₂Cu(μ-SBn)(μ-SPh)Al(SEt)(SHex) may be formed as follows.

The intermediate product (Ph₃P)₂Cu—Cl is formed as described in Example1 above (and repeated below for convenience). Two (2) molar equivalentsof Ph₃P (42.000 grams, 160.13 millimoles) may be added to a mixture oftwo hundred forty (240) milliliters (mL) of anhydrous benzene (C₆H₆) andtwo hundred forty (240) milliliters (mL) of anhydrous tetrahydrofuran((CH₂)₄O, THF) to form a first solution, which may be stirred. One (1)molar equivalent of anhydrous Cu(I)Cl (7.9260 grams, 80.064 millimoles)may be added to the stirring first solution to form a first whitesuspension including the intermediate product (Ph₃P)₂Cu—Cl. The firstsuspension may be concentrated to form a solid product or kept tocontinue the reaction, which is referred to herein as “Mixture A.”

A second solution (which is formed as described above and repeated belowfor convenience) may be formed by adding one (1) molar equivalent of Nametal (34.000 grams, 1478.9 millimoles, collected from mineral oil andwashed several times with diethyl ether) to about 500 mL of diethylether. One (1) molar equivalent of EtSH (109.52 mL, 1478.9 millimoles)may be added to the second solution and stirred for twelve (12) hours atforty (40) degrees Celsius (° C.). The EtSH and the Na metal react withone another to form NaSEt. The resulting product that includes the NaSEt(which may comprise a solution or a solid product comprising the NaSEtformed by drying a solution) is referred to herein as “Mixture B.”

A third solution (which is formed as described above and repeated belowfor convenience) may be formed by adding one (1) molar equivalent of Nametal (10.000 grams, 434.97 millimoles, collected from mineral oil andwashed several times with diethyl ether) to about 200 mL of diethylether. One (1) molar equivalent of C₆H₅CH₂SH(HSBn, 51.066 mL, 434.97millimoles) may be added to the third solution and stirred for twelve(12) hours at forty (40) degrees Celsius (° C.). The C₆H₅CH₂SH and theNa metal react with one another to form NaSCH₂C₆H₅ (NaSBn). Theresulting product that includes the NaSBn (which may comprise a solutionor a solid product comprising the NaSBn formed by drying a solution) isreferred to herein as “Mixture C.”

A fourth solution may be formed by adding one (1) molar equivalent of Nametal (10.000 grams, 434.97 millimoles, collected from mineral oil andwashed several times with diethyl ether) to about 200 mL of diethylether. One (1) molar equivalent of C₆H₅SH (HSPh, 44.454 mL, 434.97millimoles) may be added to the fourth solution and stirred for twelve(12) hours at forty (40) degrees Celsius (° C.). The C₆H₅SH and the Nametal react with one another to form NaSC₆H₅ (NaSPh). The resultingproduct that includes the NaSPh (which may comprise a solution or asolid product comprising the NaSPh formed by drying a solution) isreferred to herein as “Mixture D.”

A fifth solution may be foil led by adding one (1) molar equivalent ofNa metal (10.000 grams, 434.97 millimoles, collected from mineral oiland washed several times with diethyl ether) to about 200 mL of diethylether. One (1) molar equivalent of C₆H₁₃SH (HSHex, 61.227 mL, 434.972millimoles) may be added to the fifth solution and stirred for twelve(12) hours at forty (40) degrees Celsius (° C.). The C₆H₁₃SH and the Nametal react with one another to form NaSC₆H₁₃ (NaSHex). The resultingproduct that includes the NaSHex (which may comprise a solution or asolid product comprising the NaSHex formed by drying a solution) isreferred to herein as “Mixture E.”

A sixth solution may be fainted by adding one (1) molar equivalent ofNaSBn (8.184 grams, 80.064 millimoles) provided by Mixture C to thefirst solution ((Ph₃P)₂Cu—Cl) provided by Mixture A, after which thesixth solution may be stirred for twelve (12) hours. The (Ph₃P)₂Cu—Cland the NaSBn react with one another to form. (Ph₃P)₂CuSBn. Theresulting mixture may comprise a sixth solution. This solution maycomprise the intermediate product (Ph₃P)₂CuSBn (which may comprise asolution or a solid product comprising the (Ph₃P)₂CuSBn formed by dryinga solution) and is referred to herein as “Mixture F.”

A seventh solution may be formed by adding one (1) molar equivalentanhydrous AlCl₃ (10.676 grams, 80.064 millimoles) to the sixth solutionof (Ph₃P)₂CuSBn provided by Mixture F, after which the seventh solutionmay be stirred for about sixty (60) minutes at eighty (80) degreesCelsius (° C.). The resulting mixture is the seventh solution. Thissolution may comprise the intermediate product(Ph₃P)₂Cu(μ-SBn)(μ-Cl)Al(Cl)₂ (which may comprise a solution or a solidproduct comprising the (Ph₃P)₂Cu(μ-SBn)(μ-Cl)Al(Cl)₂ formed by drying asolution) and is referred to herein as “Mixture G.”

An eighth solution may be formed by adding one (1) molar equivalentNaSPh (10.581 grams, 80.064 millimoles) provided by Mixture D to theseventh solution of (Ph₃P)₂Cu(μ-SBn)(μ-Cl)Al(Cl)₂ provided by Mixture G,after which the eighth solution may be stirred for about sixty (60)minutes at eighty (80) degrees Celsius (° C.). The resulting mixture isthe eighth solution. This solution may comprise the intermediate product(Ph₃P)₂Cu(μ-SBn)(μ-SPh)Al(Cl)₂ (which may comprise a solution or a solidproduct comprising the (Ph₃P)₂Cu(μ-SBn)(μ-SPh)Al(Cl)₂ formed by drying asolution) and is referred to herein as “Mixture H.”

A ninth solution may be formed by adding one (1) molar equivalent NaSEt(6.735 grams, 80.064 millimoles) provided by Mixture B to the eighthsolution of (Ph₃P)₂Cu(μ-SBn)(μ-SPh)Al(Cl)₂ provided by Mixture H, afterwhich the ninth solution may be stirred for about sixty (60) minutes ateighty (80) degrees Celsius (° C.). The resulting mixture is the ninthsolution. This solution may comprise the intermediate product(Ph₃P)₂Cu(μ-SBn)(μ-SPh)Al(SEt)(Cl) (which may comprise a solution or asolid product comprising the (Ph₃P)₂Cu(μ-SBn)(μ-Ph)Al(SEt)(Cl) formed bydrying a solution) is referred to herein as “Mixture I.”

A tenth solution may be formed by adding one (1) molar equivalent NaSHex(11.227 grams, 80.064 millimoles) provided by Mixture E to the ninthsolution of (Ph₃P)₂Cu(μ-SBn)(μ-SPh)Al(SEt)(Cl) provided by Mixture I,after which the tenth solution may be stirred for about twelve (12)hours at eighty (80) degrees Celsius (° C.). After stirring, theresulting mixture may comprise a suspension that includes a solutionwith particles of the SSP (Ph₃P)₂Cu(μ-SBn)(μ-SPh)Al(SEt)(SHex) suspendedtherein. The SSP may be isolated by filtering of by-product, and thefiltrate may be concentrated as necessary or desirable. Optionally, theisolated SSP may be re-crystallized in preparation for using the SSP toform the ternary chalcopyrite material CuAlS₂.

Example 4

The SSP (Ph₃P)₂Cu(μ-SePh)₂In(SePh)₂ may be formed as follows.

One (1) molar equivalent of the SSP (Ph₃P)₂Cu(μ-SEt)₂In(SEt)₂ (10.000grams, 10.555 millimoles), which may be formed as described in Example1, may be added to about 50 mL of benzene to form a first solution,which may be stirred. Four (4) molar equivalents of C₆H₅SeH (PhSeH,4.7080 mL, 42.220 millimoles) may be added to the stirring firstsolution to form a first solution or suspension including the product(Ph₃P)₂Cu(μ-SePh)₂In(SePh)₂. The first solution or suspension may beconcentrated to form a liquid or solid product (or kept to continue thereaction as one pot reaction).

In some embodiments, however, less than four (4) molar equivalents ofthe PhSeH may initially be added to the first solution. Fractions of thefour (4) molar equivalents may be added sequentially to attain variousproducts. For example, one (1) molar equivalent of the PhSeH mayinitially be added to the first solution to form an intermediateproduct, the exact nature of which is not known, but is currentlybelieved to be the (Ph₃P)₂Cu(μ-SEt)(μ-SePh)In(SEt)₂ species. A secondmolar equivalent of the PhSeH may be added to the first solution to formanother intermediate product, the exact nature of which is not known,but is currently believed to be the (Ph₃P)₂Cu(μ-SePh)₂In(SEt)₂ species.Similarly, a third molar equivalent of the PhSeH may then be added tothe first solution to form another intermediate product, the exactnature of which is not known, but is currently believed to be the(Ph₃P)₂Cu(μ-SePh)₂In(PhSe)(SEt) species. Finally, a fourth molarequivalent of the PhSeH may be added to the first solution to form thefinal SSP product (Ph₃P)₂Cu(μ-SePh)₂In(SePh)₂.

After all four (4) molar equivalents of the PhSeH have been added to thefirst solution, the solution may be stirred for an additional one (1)hour. After stirring, the resulting mixture may comprise a solution orsuspension that includes a solution with particles of the SSP(Ph₃P)₂Cu(μ-SePh)₂In(SePh)₂ suspended therein. The SSP may be isolatedby evaporation of by-product. Optionally, the isolated SSP may bere-crystallized in preparation for using the SSP to form the ternarychalcopyrite material CuInSe₂.

It will be apparent from the above description that, in additionalembodiments, instead of using the same reagent (e.g., PhSeH) in each ofthe sequential additions to the reaction mixture, different reagentsincluding different moieties (other than phenylselenol) may be added tothe first solution to substitute different, selected moieties into theresulting SSP product at different selected locations within thestructure of the SSP molecule or complex.

In accordance with yet further embodiments of the present invention,polymeric SSPs may be formed by polymerizing SSP molecules or complexes,such as the SSP molecules or complexes formed as previously describedherein. For example, an organometallic polymeric SSP of the generalformula [L₂N(ER¹)_(a)(μ-ER²E)_(b)M′(ER¹)_(c)(ER²E)_(d)]_(m) may befabricated using Reactions 1 through 3 (which are the same as above andrepeated below for convenience) and Reaction 12 below:

N—X+2L→L₂N—X  Reaction 1

L₂N—X+M′X₃→½{L₂N(μ-X)₂M′X₂}₂  Reaction 2

½{L₂N(μ-X)₂M′X₂}₂+4MER→L₂N(μ-ER)₂M′(ER)₂(+4MX)  Reaction 3

L₂N(μ-ER)₂M′(ER)₂+nHE¹R¹E¹H→[L₂N(ER)_(a)(μ-E¹R¹E¹)_(b)M′(ER)_(c)(E¹R¹E¹)_(d)]_(m)  Reaction12

wherein L is a Lewis base (that is coordinated to N by a dative bond),each N is individually selected from Group IB atoms, each M isindividually selected from Group IA atoms, each M′ is individuallyselected from Group IIIA atoms, each E is individually selected fromGroup VIA atoms, each E¹ is individually selected from Group VIA atoms(E and E¹ may be the same or different), each X is individually selectedfrom group VIIA atoms or a nitrate group, n is any number from less thanone (1) to four (4) or excess, a is any number from zero (0) to two (2),b is the difference between two (2) and a (b=2−a), c is any number fromzero (0) to two (2), d is the difference between two (2) and c (d=2−c),the sum of b and d is equal to n (n=b+d) (if n is four (4) or less), mis any number representing the size of the resulting polymeric moleculesor complexes, each of the R groups is individually selected from thegroup consisting of alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoroaryl, silane, and carbamato groups, and each of the R¹ groups isindividually selected from the group consisting of α,ω-E¹ functionalizedalkyl, vinyl, (per)fluoro alkyl, (per)fluoro aryl, silane, and carbamatogroups.

In Reaction 12, up to four (4) units of the ER groups of theL₂N(μ-ER)₂M′(ER)₂ substance may be replaced with E′R′E′ to give linearor cross-linked polymeric SSPs. In other words, the degree ofpolymerization may be relatively higher when, for example, n is aboutfour (4), and the degree of polymerization may be relatively lower when,for example, n is about one (1) or less, with intermediate degrees ofpolymerization being attained when n has an intermediate value betweenone (1) and four (4). It is noted that the R¹ groups in the four molarequivalents of the HE¹R¹E¹H reagent may differ from one another, and maybe individually selected from the group consisting of α,ω-E¹functionalized alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl,silane, and carbamato groups. It is noted that the E¹ groups in the fourmolar equivalents of the HE¹R¹E¹H reagent may differ from one another,and may be individually selected from the Group VIA atoms.

In some embodiments, m may be one (1) or greater than one (1). Forexample, m may be between one (1) and about 20,000 or higher.

Reactions 1 through 3 may be carried out as previously described herein.Referring to Reaction 12, the non-polymeric organometallic substanceL₂N(μ-ER)₂M′(ER)₂ may be polymerized by reacting between about one (1)and about four (4) molar equivalents of HE¹R¹E¹H with theL₂N(μ-ER)₂M′(ER)₂ substance to form a polymeric organometallic SSP ofthe empirical formula[L₂N(ER)_(a)(μ-E¹R¹E¹)_(b)M′(ER)_(c)(E¹R¹E¹)_(d)]_(m). Reaction 12 maybe carried out in a solution comprising benzene (C₆H₆) or a mixture ofmore than one solvent or another suitable solvent.

Example 5

As a non-limiting example, one (1) molar equivalent of(Ph₃P)₂Cu(μ-SEt)₂In(SEt)₂ (20.000 grams, 21.110 millimoles), which maybe formed as previously described in Example 1, may be added to about100 mL of benzene to form a first solution, which may be stirred. Four(4) molar equivalents of HSCH₂CH₂SH (HSEtSH, 7.0821 mL, 84.438millimoles) may be added to the stirring first solution to form a firstsuspension including the product[(Ph₃P)₂Cu(μ-SCH₂CH₂S)₂In(SCH₂CH₂S)₂]_(m), where m may be between one(1) and about 20,000 or higher. The first suspension may be concentratedto form a solid product (or kept to continue the reaction as in a onepot reaction).

In some embodiments, two or more different SSPs (e.g., containingdifferent N and/or M′ atoms) may be polymerized by reacting betweenabout one (1) and about four (4) or excess molar equivalents of HE¹R¹E¹Hwith the two or more different SSPs to form copolymeric organometallicSSPs of the empirical formula{[L₂N¹(ER)_(a)(μ-E¹R¹E¹)_(b)M′¹(ER)_(c)(E¹R¹E¹)_(d)]_(m)[L₂N²(ER)_(e)(μ-E¹R¹E¹)_(f)M′²(ER)_(g)(E¹R¹E¹)_(h)]_(n)}_(l),wherein L is a Lewis base coordinated to N¹ and N² by a dative bond,each N¹ and N² is individually selected from Group IB atoms (N¹ and N²may be the same or different), each M′¹ and M′² is individually selectedfrom Group IIIA atoms (M′¹ and M′² may be the same or different), each Eand E¹ is individually selected from Group VIA atoms (E and E¹ may besame or different), a is any number from zero (0) to two (2), b is thedifference between two (2) and a (b=2−a), c is any number from zero (0)to two (2), d is the difference between two (2) and c (d=2−c), m is anynumber, e is any number from zero (0) to two (2), f is the differencebetween two (2) and e (f=2−e), g is any number from zero (0) to two (2),h is the difference between two (2) and g (h=2−g), n is any number, l isany number, each R group is individually selected from the groupconsisting of alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl,silane, and carbamato groups, and each of the R¹ groups is individuallyselected from the group consisting of α,ω-E¹ functionalized alkyl, aryl,vinyl, (per)fluoro alkyl, (per)fluoro aryl, silane, and carbamatogroups. It is noted that the R¹ groups in the four molar equivalents ofthe HE¹R¹E¹H reagent may differ from one another, and may beindividually selected from the group consisting of alkyl, aryl, vinyl,(per)fluoro alkyl, (per)fluoro aryl, silane, and carbamato groups. It isnoted that the E¹ groups in the four molar equivalents of the HE¹R¹E¹Hreagent may be the same or different from one another, and may beindividually selected from the Group VIA atoms. It is noted that allpossible variations in identities and quantities of different SSPs canbe used to form copolymeric single source precursors.

In some embodiments, m, n, and l may be one (1) or greater than one (1).For example, in, n, and l may be between one (1) and about 20,000 orhigher (m, n, and/may be the same or different from one another).

Example 6

As a non-limiting example, one (1) molar equivalent of(Ph₃P)₂Cu(μ-SEt)₂In(SEt)₂ (10.000 grams, 10.555 millimoles) and one (1)molar equivalent of (Ph₃P)₂Cu(μ-SEt)₂Ga(SEt)₂ (9.5240 grams, 10.555millimoles), which may be provided using methods previously describedherein, may be added to about 100 mL of benzene to form a firstsolution, which may be stirred. Eight (8) molar equivalents ofHSCH₂CH₂SH(HSEtSH, 7.0821 mL, 84.438 millimoles) may be added to thestirring first solution to forth a copolymeric, organometallic SSPhaving the empirical equation{[(Ph₃P)₂Cu(μ-SCH₂CH₂S)₂In(SCH₂CH₂S)₂]_(m)[(Ph₃P)₂Cu(μ-SCH₂CH₂S)₂Ga(SCH₂CH₂S)₂]_(n)}_(l),where m, n, and l may be between one (1) and about 20,000 or higher. Thefirst suspension may be concentrated to form a solid product (or kept tocontinue the reaction as in a one pot reaction).

Example 7

As a non-limiting example, one (1) molar equivalent of(Ph₃P)₂Cu(μ-SEt)₂In(SEt)₂ (10.000 grams, 10.555 millimoles), and one (1)molar equivalent of (Ph₃P)₂Ag(μ-SEt)₂Ga(SEt)₂ (9.9919 grams, 10.555millimoles), which may be provided using methods previously describedherein, may be added to about 100 mL of benzene to form a firstsolution, which may be stirred. Eight (8) molar equivalents ofHSCH₂CH₂SH(HSEtSH, 7.0821 mL, 84.438 millimoles) may be added to thestirring first solution to form a copolymeric, organometallic SSP havingthe empirical formula{[(Ph₃P)₂Cu(μ-SCH₂CH₂S)₂In(SCH₂CH₂S)₂]_(m)[(Ph₃P)₂Ag(μ-SCH₂CH₂s)₂Ga(SCH₂CH₂S)₂]_(n)}_(l),where m, n, and l may be between one (1) and about 20,000 or higher. Thefirst suspension may be concentrated to form a solid product (or kept tocontinue the reaction as in a one pot reaction).

In accordance with some embodiments of the present invention, acopolymeric, organometallic SSP may be formed using methods describedherein that includes two or more Group I metals, two or more Group IIImetals, and/or two or more Group VIA elements. For example, an SSPhaving the following formula may be formed in accordance with someembodiments of the present invention:{[(Ph₃P)₂Cu(μ-SCH₂CH₂S)₂In(SCH₂CH₂S)₂—]_(m)[(Ph₃P)₂Cu(μ-SCH₂CH₂S)₂Ga(SCH₂CH₂S)₂]_(m)[(Ph₃P)₂Cu(μ-SCH₂CH₂S)₂Al(SCH₂CH₂S)₂—]_(m)[(Ph₃P)₂Ag(μ-SCH₂CH₂S)₂In(SCH₂CH₂S)₂]_(m)[(Ph₃P)₂Ag(μ-SCH₂CH₂S)₂Ga(SCH₂CH₂S)₂—]_(m)[(Ph₃P)₂Ag(μ-SCH₂CH₂S)₂Al(SCH₂CH₂S)₂]_(m)}_(m),wherein each m may be between one (1) and about 20,000 or higher.

In some embodiments, two or more different HE¹R¹E¹H species may bereacted with one or more than one L₂N(μ-ER)₂M′(ER)₂ species in apolymerization reaction to form a copolymeric organometallic SSP havingthe empirical formula{[L₂N¹(μ-ER)_(a)(μ-E¹R¹E¹)_(b)M′¹(ER)_(c)(E¹R¹E¹)_(d)]_(m)[L₂N²(μ-ER)_(e)(μ-E¹R¹E¹)_(f)M′²(ER)_(g)(E¹R¹E¹)_(h)]_(n)}_(l).

In some embodiments, one or more different HE¹R¹E¹H species and one ormore different HE²R² species may be reacted with one or more differentL₂N(μ-ER)₂M′(ER)₂ species to form a polymeric organometallic SSP of theempirical formula{[L₂N(E²R²)_(a)(μ-E¹R¹E¹)_(b)M′(E²R²)_(c)(E¹R¹E¹)_(d)]_(m). It is notedthat the E, E¹, and E² atoms in the reagents may be the same ordifferent, and may be individually selected from the Group VIA atoms.

Example 8

As a non-limiting example, one (1) molar equivalent of(Ph₃P)₂Cu(μ-SEt)₂In(SEt)₂ (10.000 grams, 10.555 millimoles), which maybe provided using methods previously described herein, may be added toabout 100 mL of benzene to form a first solution, which may be stirred.Four (4) molar equivalent of C₆H₅SeH (PhSeH, 4.4837 mL, 42.220millimoles) and one (1) molar equivalent of HSCH₂CH₂SH(HSEtSH, 0.88530mL, 10.555 millimoles) may be added to the stirring first solution toform copolymeric organometallic SSPs having the empirical formula[(Ph₃P)₂Cu(μ-SCH₂CH₂S)(μ-SePh)In(SePh)₂]_(m) or[(Ph₃P)₂Cu(μ-SePh)₂In(SePh)(SCH₂CH₂S)]_(m), where m may be between one(1) and about 20,000 or higher. The first suspension may be concentratedto form a solid product (or kept to continue the reaction as in a onepot reaction).

In accordance with additional embodiments of the present invention, apolymeric SSP of the general formula[L₂N(ER)_(a)(μ-E¹R¹E¹)_(b)M′(ER)_(c)(E¹R¹E¹)_(d)]_(m), may be fabricatedusing Reactions 1 and 2 (which are the same as above and repeated belowfor convenience), and additional Reaction 13 below:

N—X+2L→L₂N—X  Reaction 1

L₂N—X+M′X₃→¼{L₂N(μ-X)₂M′X₂}₂  Reaction 2

½{L₂N(μ-X)₂M′X₂}₂+nME¹R¹E¹M+pMER→[L₂N(ER)_(a)(μ-E¹R¹E¹)_(b)M′(ER)_(c)(E¹R¹E¹)_(d)]_(m)(+4MX)  Reaction13

wherein L is a Lewis base that is coordinated to N by a dative bond,each N is individually selected from Group IB atoms, each M isindividually selected from Group IA atoms, each M′ is individuallyselected from Group IIIA atoms, each X is individually selected fromGroup VITA atoms or a nitrate group, each E and E¹ is individuallyselected from Group VIA atoms (E and E¹ may be the same or different), nis any number from one (1) to four (4), p is the difference between four(4) and n (p=4−n), a is any number from zero (0) to two (2), b is thedifference between two (2) and a (b=2−a), c is any number from zero (0)to two (2), d is the difference between two (2) and c (d=2−c), the sumof b and d is equal to n (n=b+d), the sum of a and c is equal top(p=a+c), m is any number representing the size of the resultingpolymeric molecules or complexes, each of the R groups is individuallyselected from the group consisting of alkyl, aryl, vinyl, (per)fluoroalkyl, (per)fluoro aryl, silane, and carbamato groups, and each of theR¹ groups is individually selected from the group consisting of α,ω-E¹functionalized alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl,silane, and carbamato groups. In some embodiments, m may be one (1) orgreater than one (1). For example, r n may be between one (1) and about20,000 or greater.

Reactions 1 and 2 may be carried out as previously described herein.Referring to Reaction 13, the non-polymeric organometallic substanceL₂N(μ-X)₂M′(X)₂ may be polymerized by reacting between about one (1) andabout four (4) molar equivalents of ME¹R¹E¹M and MER (eithersequentially or simultaneously) with the L₂N(μ-X)₂M′(X)₂ substance toform a polymeric organometallic SSP of the empirical formula[L₂N(ER)_(a)(μ-E¹R¹E¹)_(b)M′(ER)_(c)(E¹R¹E¹)_(d)]_(m). Reaction 13 maybe carried out in a solution comprising benzene (C₆H₆) or anothersuitable solvent or solvent mixture.

Example 9

As a non-limiting example, one (1) molar equivalent of½{(Ph₃P)₂Cu(μ-Cl)₂In(Cl)₂}₂ (67.635 grams, 80.064 millimoles), which maybe provided using methods previously described herein, may be added to amixture of about 240 mL of anhydrous benzene and 240 mL of anhydrous THFto form a first solution, which may be stirred. About two (2) molarequivalents of NaSCH₂CH₂SNa (22.123 grams, 160.128 millimoles) and abouttwo (2) molar equivalents of NaSEt (13.470 mL, 160.128 millimoles) maybe added to the stirring first solution to form a polymeric,organometallic SSP having the empirical formula[(Ph₃P)₂Cu(μ-(SCH₂CH₂S))(μ-SEt)In(SCH₂CH₂S)(SEt)]_(m), where m may bebetween one (1) and about 20,000 or higher.

In some embodiments, two or more different L₂N(μ-X)₂M′(X)₂ species maybe polymerized by reacting between about one (1) and about four (4)molar equivalents of ME¹R¹E¹M and MER (either sequentially orsimultaneously) with the two or more different L₂N(μ-X)₂M′(X)₂ speciesto form a copolymeric organometallic SSP of the empirical formula{[L₂N¹(ER)_(a)(μ-E¹R¹E¹)_(b)M′¹(ER)_(c)(E¹R¹E¹)_(d)]_(m)[L₂N²(ER)_(e)(μ-E¹R¹E¹)_(f)M′²(ER)_(g)(E¹R¹E¹)_(h)]_(n)}_(l),wherein L is a Lewis base that is coordinated to N¹ and N² by dativebonds, each N¹ and N² is individually selected from Group IB atoms (N¹and N² may be the same or different), each M is individually selectedfrom Group IA atoms, each M′¹ and M′² is individually selected fromGroup IIIA atoms (M′¹ and M′² may be the same or different), each E andE¹ is individually selected from Group VIA atoms (E and E¹ may be thesame or different), each X is individually selected from Group VIIAatoms or a nitrate group, a is any number from zero (0) to two (2), b isthe difference between two (2) and a (b=2−a), c is any number from zero(0) to two (2), d is the difference between two (2) and c (d=2−c), m isany number, e is any number from zero (0) to two (2), f is thedifference between two (2) and e (f=2−e), g is any number from zero (0)to two (2), h is the difference between two (2) and g (h=2−g), n is anynumber, l is any number, each of the R groups is individually selectedfrom the group consisting of alkyl, aryl, vinyl, (per)fluoro alkyl,(per)fluoro aryl, silane, and carbamato groups, and each of the R¹groups is individually selected from the group consisting of α,ω-E¹functionalized alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl,silane, and carbamato groups. It is noted that the E¹ groups in the fourmolar equivalents of the ME¹R¹E¹M reagent may differ from one another,and may be individually selected from the Group VIA atoms. It is notedthat all possible variations in identities and quantities of anyorganometallic substance can be used to form copolymeric single sourceprecursors. In some embodiments, m, n, and l may be one (1) or greaterthan one (1). For example, m, n, and l may be between one (1) and about20,000 or higher (m, n, and l may be the same or different).

Example 10

As a non-limiting example, one (1) molar equivalent of½{(Ph₃P)₂Cu(μ-Cl)₂In(Cl)₂}₂ (33.818 grams, 40.032 millimoles) and one(1) molar equivalent of ½{(Ph₃P)₂Cu(μ-Cl)₂Ga(Cl)₂}₂ (32.012 grams,40.032 millimoles), which may be formed using methods previouslydescribe herein, may be added to a mixture of about 240 mL of anhydrousbenzene and 240 mL of anhydrous THF to form a first solution, which maybe stirred. About two (2) molar equivalents of NaSCH₂CH₂SNa (22.123grams, 160.128 millimoles) and about two (2) molar equivalents of NaSEt(13.470 mL, 160.128 millimoles) may be added to the stirring firstsolution to form a copolymeric, organometallic SSP having the empiricalequation{[(Ph₃P)₂Cu(μ-(SCH₂CH₂S))(μ-SEt)In(SCH₂CH₂S)(SEt)]_(m)[(Ph₃P)₂Cu(μ-(SCH₂CH₂S))(μ-SEt)Ga(SCH₂CH₂S)(SEt)]_(n)}_(l), where m, n, and l may be between one (1) and about20,000 or higher. The first suspension may be concentrated to form asolid product (or kept to continue the reaction as one pot reaction).

Example 11

As a non-limiting example, one (1) molar equivalent of½{(Ph₃P)₂Cu(μ-Cl)₂In(Cl)₂}₂ (33.818 grams, 40.032 millimoles) and one(1) molar equivalent of ½{(Ph₃P)₂Cu(μ-Cl)₂Ga(Cl)₂}₂ (32.012 grams,40.032 millimoles), which may be provided using methods previousdescribed herein, may be added to a mixture of about 240 mL of anhydrousbenzene and 240 mL of anhydrous THF to form a first solution, which maybe stirred. About four (4) molar equivalents of NaSCH₂CH₂SNa (NaSEtSNa,44.246 grams, 320.256 millimoles) may be added to the stirring firstsolution to form a copolymeric, organometallic SSP having the empiricalformula{[(Ph₃P)₂Cu(μ-(SEtS))₂In(SEtS)₂]_(m)[(Ph₃P)₂Cu(μ-(SEtS))₂Ga(SEtS)₂)]_(n)}_(l),where m, n, and l may be between one (1) and about 20,000 or higher. Thefirst suspension may be concentrated to form a solid product (or kept tocontinue the reaction as a one pot reaction).

In some embodiments, two or more different ME¹R¹E¹M and MER species maybe polymerized by reacting between one or more than one of theL₂N(μ-X)₂M′(X)₂ species to form a copolymeric organometallic SSP of theempirical formula{[L₂N¹(ER)_(a)(μ-E¹R¹E¹)_(b)M′¹(ER)_(c)(E¹R¹E¹)_(d)]_(m)[L₂N²(ER)_(c)(μ-E¹R¹E¹)_(f)M′²(ER)_(g)(E¹R¹E¹)_(h)]_(n)}_(l).

Using the polymerization reactions described above, new polymeric,organometallic SSPs having the empirical formula[L₂N(ER)_(a)(μ-E¹R¹E¹)_(b)M′(ER)_(e)(E¹R¹E¹)_(d)]_(m), may be provided,wherein each of a, b, c, and d are between zero (0) and two (2). Forexample, in some embodiments, the SSPs may have the empirical formula[L₂N(μ-ER)(μ-E¹R¹E¹)M′(ER)_(c)(E¹R¹E¹)_(d)]_(m). In additionalembodiments, the SSPs may have the empirical formula[L₂N(μ-E¹R¹E¹)₂M′(ER)_(c)(E¹R¹E¹)_(d)]_(m). In additional embodiments,the SSPs may have the empirical formula[L₂N(ER)_(a)(μ-E¹R¹E¹)_(b)M′(ER)(E¹R¹E¹)]_(m). In yet furtherembodiments, the SSPs may have the empirical formula[L₂N(ER)_(a)(μ-E¹R¹E¹)_(b)M′(E¹R¹E¹)₂]_(m).

In some embodiments, the polymeric, organometallic SSPs may comprisesubstantially linear polymeric molecules or complexes. In additionalembodiments, the polymeric, organometallic SSPs may comprisecross-linked substantially linear polymeric molecules or complexes. Inyet further embodiments, the cross-linking between the individual SSPmolecules or complexes may be so extensive that the polymeric,organometallic SSPs have a three-dimensional network structure.

The reaction pathways disclosed herein for forming SSPs allow thedifferent R groups in the SSPs, as well as the different E, N, and M′atoms, to be selectively and individually tailored, which further allowschemical and physical properties of the SSPs, such as, for example,reactivity, solubility, melting point, boiling point, etc., to beselectively tailored.

SSPs (including polymeric SSPs and non-polymeric SSPs) made inaccordance with embodiments of the present invention may be used to formchalocogenide materials (e.g., semiconductive ternary chalcopyritematerials) using methods such as, for example, those disclosed in U.S.patent application Ser. No. 12/047,956, filed Mar. 13, 2008, now U.S.Pat. No. 8,003,070, issued Aug. 23, 2011 to Fox et al., the disclosureof which is incorporated herein in its entirety by this reference.

Semiconductor materials and particles fabricated using SSPs formulatedin accordance with embodiments of methods of the present invention maybe used in many different types of semiconductor devices. For example,semiconductor materials and particles formed using embodiments ofmethods of the present invention may be used in semiconductor devicessuch as, for example, diodes (e.g., light emitting diodes (LEDs)),photovoltaic devices, sensors, solid state lasers, and integratedcircuits (e.g., memory modules and microprocessors).

While the invention may be susceptible to various modifications andalternative forms, specific embodiments have been shown by way ofexample and have been described in detail herein. However, it should beunderstood that the invention is not intended to be limited to theparticular forms disclosed. Rather, the invention includes allmodifications, equivalents, and alternatives falling within the scope ofthe invention as defined by the following appended claims and theirlegal equivalents.

1. A method of forming a copolymeric single source precursor, comprisingreacting a first single source precursor, a second single sourceprecursor differing from the first single source precursor, and HE¹R¹E¹Hto form a copolymeric single source precursor having the empiricalformula{[L₂N¹(ER)_(a)(μ-E¹R¹E¹)_(b)M′¹(ER)_(c)(E¹R¹E¹)_(d)]_(m)[L₂N²(ER)_(e)(μ-E¹R¹E¹)_(f)M′²(ER)_(g)(E¹R¹E¹)_(h)]_(n)}_(l),wherein L is a Lewis base, each N¹ and N² is individually selected fromGroup IB atoms, each M′¹ and M′² is individually selected from GroupIIIA atoms, each E and E¹ is individually selected from Group VIA atoms,a is any number from zero (0) to two (2), b is the difference betweentwo (2) and a, c is any number from zero (0) to two (2), d is thedifference between two (2) and c, e is any number from zero (0) to two(2), f is the difference between two (2) and e, g is any number fromzero (0) to two (2), h is the difference between two (2) and g, m is anynumber, n is any number, l is any number, each R is individuallyselected from the group consisting of alkyl, aryl, vinyl, (per)fluoroalkyl, (per)fluoro aryl, silane, and carbamato groups, and each R¹ isindividually selected from the group consisting of α,ω-E¹ functionalizedalkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl, silane, andcarbamato groups.
 2. A method of forming a copolymeric single sourceprecursor, comprising reacting uME¹R¹E¹M and vMER with a first substancehaving the empirical formula L₂N¹(μ-X)₂M′¹(X)₂ and a second substancehaving the empirical formula L₂N²(μ-X)₂M′²(X)₂ to form a copolymericsingle source precursor having the empirical formula{[L₂N¹(ER)_(a)(μ-E¹R¹E¹)_(b)M′¹(ER)_(c)(E¹R¹E¹)_(d)]_(m)[L₂N²(ER)_(e)(μ-E¹R¹E¹)_(f)M′²(ER)_(g)(E¹R¹E¹)_(h)]_(n)}_(l),wherein L is a Lewis base, each X is individually selected from GroupVIIA atoms or a nitrate group, each N¹ and N² is individually selectedfrom Group IB atoms, each M′¹ and M′² is individually selected fromGroup IIIA atoms, each E and E¹ is individually selected from Group VIAatoms, a is any number from zero (0) to two (2), b is the differencebetween two (2) and a, c is any number from zero (0) to two (2), d isthe difference between two (2) and c, e is any number from zero (0) totwo (2), f is the difference between two (2) and e, g is any number fromzero (0) to two (2), h is the difference between two (2) and g, m is anynumber, n is any number, l is any number, u is any number from zero (0)to four (4), v is the difference between four (4) and u, each R isindividually selected from the group consisting of alkyl, aryl, vinyl,(per)fluoro alkyl, (per)fluoro aryl, silane, and carbamato groups, andeach R¹ is individually selected from the group consisting of α,ω-E¹functionalized alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl,silane, and carbamato groups.
 3. The method of claim 1, where at leasttwo R¹ groups in the copolymeric single source precursor differ from oneanother.
 4. The method of claim 1, wherein at least two E¹ groups in thecopolymeric single source precursor differ from one another.
 5. Themethod of claim 1, wherein the R¹ groups in the copolymeric singlesource precursor are the same.
 6. The method of claim 1, wherein the E¹groups in the copolymeric single source precursor are the same.
 7. Themethod of claim 1, wherein m is between one and 20,000.
 8. The method ofclaim 1, wherein n is between one and 20,000.
 9. The method of claim 1,wherein/is between one and 20,000.
 10. The method of claim 1, wherein atleast one of m, n, and l is greater than 20,000.
 11. The method of claim1, further comprising selecting the first single source precursor tocomprise a substance having the empirical formula L₂N¹(μ-X)₂M′¹(X)₂ andselecting the second single source precursor to comprise a substancehaving the empirical formula L₂N²(μ-X)₂M′²(X)₂.
 12. The method of claim11, wherein at least some N¹ atoms differ from at least some N² atoms inthe copolymeric single source precursor.
 13. The method of claim 11,wherein at least some M′¹ atoms differ from at least some M′² atoms inthe copolymeric single source precursor.
 14. The method of claim 2,where at least two R¹ groups in the copolymeric single source precursordiffer from one another.
 15. The method of claim 2, wherein at least twoE¹ groups in the copolymeric single source precursor differ from oneanother.
 16. The method of claim 2, wherein the E¹ groups in thecopolymeric single source precursor are the same.
 17. The method ofclaim 2, wherein at least one of m, n, and l is between one and 20,000.18. The method of claim 2, wherein at least one of m, n, and l isgreater than 20,000.
 19. The method of claim 2, wherein at least some N¹atoms differ from at least some N² atoms in the copolymeric singlesource precursor.
 20. The method of claim 2, wherein at least some M′¹atoms differ from at least some M′² atoms in the copolymeric singlesource precursor.